EP0385748B1 - Agglomerate zum Mischen mit Reinigungspulvern - Google Patents

Agglomerate zum Mischen mit Reinigungspulvern Download PDF

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Publication number
EP0385748B1
EP0385748B1 EP90302125A EP90302125A EP0385748B1 EP 0385748 B1 EP0385748 B1 EP 0385748B1 EP 90302125 A EP90302125 A EP 90302125A EP 90302125 A EP90302125 A EP 90302125A EP 0385748 B1 EP0385748 B1 EP 0385748B1
Authority
EP
European Patent Office
Prior art keywords
agglomerate
agglomerates
particulate material
clay
weight
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.)
Expired - Lifetime
Application number
EP90302125A
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English (en)
French (fr)
Other versions
EP0385748A3 (de
EP0385748A2 (de
Inventor
William Derek Emery
Francois Delwel
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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Filing date
Publication date
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0385748A2 publication Critical patent/EP0385748A2/de
Publication of EP0385748A3 publication Critical patent/EP0385748A3/de
Application granted granted Critical
Publication of EP0385748B1 publication Critical patent/EP0385748B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • 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
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/1253Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/126Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
    • 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
    • C11D3/395Bleaching agents
    • 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
    • C11D17/06Powder; Flakes; Free-flowing mixtures; Sheets

Definitions

  • This invention relates to an agglomerated composition of improved colour and in particular to white agglomerates of clay fabric softener for addition to white or differently coloured detergent base powders.
  • Detergent powders without added colour are generally white or near-white in colour, but some ingredients especially certain classes of fabric softening clay, enzyme granules or bleach precursors may be brown, yellow or grey. The incidence of such discoloured particles in a finished detergent powder can give the whole product an off-white unattractive appearance.
  • GB 2 199 338 (Unilever Plc) proposes the use of large vividly coloured particles ("speckles") in detergent powder to render the presence of slightly discoloured particles unnoticeable.
  • GB 2 121 843 (Colgate-Palmolive Co) proposes incorporating dyes or pigments in a liquid agglomerating spray used in the manufacture of bentonite clay agglomerates to form clay speckles.
  • speckles may not be desirable or may be ineffective in camouflaging the discoloured particles.
  • a first aspect of the present invention accordingly provides a clay agglomerate selected from:
  • the invention provides a fabric softener comprising clay agglomerates, said agglomerates comprising whitening particulate material of average particle size less than 20 microns, a bulk density of less than 400 grams per litre and a reflectance value (R infinity 460) of greater than 85.
  • agglomerates of the first aspect comprising sufficient whitening particulate material to give the agglomerate an R infinity 460 value greater than 75.
  • the agglomerates of improved colour can be formed either as a cogranulate with the whitening particulate material or as agglomerates coated with the whitening particulate material.
  • the cogranulated agglomerates comprise from 30% to 60% by weight of the particulate material, more preferably from 40% to 50% by weight.
  • the average particle size of the particulate material is preferably less than 15 microns, more preferably less than 10 microns.
  • the bulk density of the particulate material is preferably less than 250 grams per litre.
  • the reflectance value measured as R infinity 460 is preferably greater than 95.
  • the particulate material When the particulate material is present as a coating on the agglomerates it comprises from 10 to 40% by weight of the total agglomerate composition. More preferably the particulate material comprises from 15 to 25% by weight of the total agglomerate composition.
  • the particulate material is preferably a precipitated calcium carbonate or a silica.
  • the precipitated calcium carbonate employed can be in the form of particles of average particle size of the order of 4 microns, built up from trigonal or aragonite crystals.
  • the silica employed is in the form of a precipitated amorphous powder of particle size of the order of 10 microns.
  • a type of precipitated calcium carbonate which is most useful in whitening the agglomerates is that which is known as SOCAL U3 (ex Solvay).
  • a type of silica which is most useful in whitening the agglomerates is that which is known as Microsil (ex Crosfields).
  • Clay softeners are well-known in the detergent patent literature. Included among such clay softeners are various heat-treated kaolins and various multi-layer smectites. GB 1 400 898 (Procter and Gamble) suggests the use of smectite clays having a relatively high exchange capacity. There is a desire to boost the performance of fabric softening clays in the wash and according to our copending patent application EP 287 344 it has been found that if certain nonionic surfactant materials are carried on the clay, at a specified level relative thereto, and the moisture content of the composition is controlled, the fabric softening performance is enhanced.
  • the examples of the invention included herein are directed towards clay carrying a nonionic surfactant but it should be understood that the invention is not limited to clays.
  • the moisture content of clay agglomerates must be between 7.5% and 12% by weight, preferably from 8% to 10%.
  • moisture in this context is not necessarily the total water content, but rather it is the water which is lost from the composition by drying in a static environment at 135°C to a constant weight.
  • the clay/nonionic agglomerates will have a higher moisture content, such as, for example from 10% to 16% moisture, and will therefore be too sticky for use, so that some post drying is necessary.
  • a drying air temperature of 85-90°C has been found to be suitable.
  • agglomerates are to be coated with precipitated calcium carbonate it may be desirable to "over-dry" the agglomerates so that moisture accommodated by the agglomerates as a result of the coating process leaves the agglomerates with a final moisture content in the desired range.
  • the nonionic surfactant system exists as a cloudy phase in the temperature range of 0°C to 80°C, preferably 0°C to 15°C in distilled water at 1% concentration.
  • the system has a cloud point of not more than 80°C, preferably not more than 15°C.
  • the cloud point correlates approximately to the hydrophilic-lipophilic balance (HLB) of the surfactant system and it is therefore preferred that the HLB should be less than 13.5, such as not more than 12.0, ideally less than 9.5.
  • the HLB should be above 6.0, preferably above 8.0 to provide sufficient detergency.
  • nonionic surfactants are alkyl (C6-C22) phenols-ethylene oxide condensates, the condensation products of aliphatic (C8-C18) primary or secondary linear or branched alcohols with ethylene oxides, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine.
  • the clay softener may be any such material capable of providing a softening benefit.
  • the effectiveness of a clay material as a fabric softener will depend on the level of smectite clay. It is preferred that the ratio of the clay to the nonionic surfactant in the agglomerate is from 3:1 to 20:1, most preferably 4:1 to 10:1.
  • Suitable binders include copolymers of polyacrylate and maleic anhydride, polyacrylates, sugars, nonionic surfactants, polyethylene glycol, polyoxyethylene alkyl ether, fatty acid monoethanolamide, carboxymethyl cellulose, soap and latex.
  • the agglomerates can be made by known granulation processes typically by those described in GB 2 121 843B.
  • the cogranulated agglomerates can be made in any granulater where the binding material can be contacted with materials to be agglomerated; preferably a high shear, short residence time granulator, such as a Schugi Flexomix or a L ödige Recycler, or a longer residence time, low shear granulater, such as a continuous drum granulater, Eirich pan granulater or a drum or cement mixer.
  • the coated agglomerates can be made in any suitable device such as a rotary drum, pan or marumeriser mixer using agglomerates made by a known granulation process.
  • agglomerates are to be coated with the particulate material
  • a preferred process for forming coated agglomerates comprises granulating the agglomerates with an excess of nonionic surfactant in a drum mixer to form "sticky" granules followed by coating with the particulate material.
  • the advantages of this process are that an improved coating adherence and colour is obtained.
  • the especially improved colour is thought to be due to the fact that no binder is present at the light scattering surface of the agglomerate.
  • a particularly preferred binder is Sokalan CP5 (ex BASF) a copolymer of maleic anhydride and polyacrylate supplied as a 40% aqueous solution.
  • a plasticiser to improve the friability resistance of the coating.
  • sorbitol or glycerol to the binder spray greatly decreases the friability of the agglomerate, especially if the agglomerate is air dried.
  • a detergent active material this may be selected from nonionic detergent active materials, anionic detergent active materials, zwitterionic or amphoteric detergent active materials or mixtures thereof.
  • the anionic detergent active materials are usually water-soluble alkali metal salts of 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 acyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C8-C18) alcohols produced for example from tallow or coconut oil, sodium and potassium alkyl (C9-C20) benzene sulphonates, particularly sodium linear secondary alkyl (C10-C15) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C8-C18) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane monos
  • the fabric washing products contain a detergency builder material this may be any material capable of reducing the level of free calcium ions in the wash liquor and will preferably provide the composition with other beneficial properties such as the generation of an alkaline pH, the suspension of soil removed from the fabric and the dispersion of the fabric softening clay material.
  • Examples of phosphorus-containing inorganic detergency builders when present, include the water-soluble salts, especially alkaline metal pyrophosphate, orthophosphates, polyphosphates and phosphonates.
  • Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates and hexametaphosphates.
  • non-phosphorus-containing inorganic detergency builders when present, include water-soluble alkali metal carbonates, bicarbonates, silicates and crystalline and amorphous alumino silicates. Specific examples include sodium carbonate (with or without calicte seeds), potassium carbonate, sodium and potassium bicarbonates and silicates.
  • organic detergency builders when present, include the alkaline metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl carboxylates and polyhydroxsulphonates. Specific examples include sodium, potassium lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids and citric acid.
  • ingredients already mentioned may also be present, either as part of the clay containing compositions or as part of the overall fabric washing product.
  • ingredients which may be present in the composition include the lather boosters, lather depressants, oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach percursors, chlorine-releasing bleaching agents such as tricloroisocyanuric acid, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes, enzymes such as proteases, lipalases, cellulases and amylases, germicides and colourants.
  • oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate
  • peracid bleach percursors peracid bleach percursors
  • chlorine-releasing bleaching agents such as tricloroisocyanuric acid
  • inorganic salts such as sodium sulphate
  • fluorescent agents such as fluorescent agents, perfumes, enzymes such as proteases, lipalases, cellulases and amylases, germicides and colourants.
  • agglomerates When the agglomerates are included in a detergent base powder they are typically present at a level from 5 to 20% by weight.
  • a typical formulation is as follows: Parts by weight Lauryl alkyl sulphonate 6 Nonionic detergent active 3 Soap 1.5 Zeolite 22 Sokalan CP5 3 Alkaline silicate 0.5 Perborate Monohydrate 7.5 TAED 1.8 Savinase 0.35 Carbonate 10.00 EDTA 0.15 Sulphate 24.39 SCMC 0.50 Clay agglomerates 10.00 Water, perfume, minors 9.31
  • Clay/nonionic agglomerates were prepared by spraying 83 parts by weight of clay (KBU, clay of cec ⁇ 50 meq/100g ex Colin Stewart Minerals) with 17 parts of Synperonic A3 (a nonionic surfactant ex ICI which is a C13-C15 alcohol ethoxylated with approximately 3 moles of ethylene oxide per molecule and having a cloud point below 0°C) in a drum mixer.
  • KBU clay of cec ⁇ 50 meq/100g ex Colin Stewart Minerals
  • Synperonic A3 a nonionic surfactant ex ICI which is a C13-C15 alcohol ethoxylated with approximately 3 moles of ethylene oxide per molecule and having a cloud point below 0°C
  • the agglomerates were tumbled in a drum coater with 20% by weight of Socal U3 (precipitated calcium carbonate ex SOLVAY having a bulk density of 230 g/l a particle size of 4 microns, and an R infinity 460 of 96) and 20% by weight of a 25% solution of Sokalan CP5.
  • Socal U3 precipitated calcium carbonate ex SOLVAY having a bulk density of 230 g/l a particle size of 4 microns, and an R infinity 460 of 96
  • the moisture content of the agglomerates as made was 18%, these were dried to a moisture content of 8%.
  • Example 1A was repeated excepting that the agglomerates were coated with 10% by weight Microsil a silica (ex Crosfields) having a particle size of 10-15 microns, a bulk density of 130 g/l and a reflectance value (R infinity 460) of 98.4.
  • Microsil a silica ex Crosfields
  • R infinity 460 reflectance value
  • Example 1 was repeated excepting that the agglomerates were coated with 20% by weight Durcal, a calcite (ex Omya) having a bulk density of 670 g/l a particle size of 4 microns and a reflectance value (R infinity 460) of 93.
  • Durcal a calcite (ex Omya) having a bulk density of 670 g/l a particle size of 4 microns and a reflectance value (R infinity 460) of 93.
  • Example 1 was repeated excepting that the agglomerates were coated with 20% by weight Speswhite, a kaolinite ex English China Clays Ltd (ECC).
  • Speswhite has a bulk density of 425 g/l, a particle size of 80% less than 2 microns and a reflectance value R infinity 460 of 85.
  • Clay/nonionic/precipitated calcium carbonate agglomerates were prepared by co-granulating 83 parts by weight of clay ('KBU) with 83 parts by weight Socal U3 using 24 parts by weight of Synperonic A3 and 62 parts by weight of a 2% solution of Sokalan CP5 as a granulating spray.
  • the agglomerates were then dried to a moisture content of approximately 8% on a fluidised bed dryer using drying air having a temperature of 80°C.
  • Example 4 was repeated excepting that the agglomerates were cogranulated with 83 parts by weight Speswhite a kaolin ex ECC in place of the Socal U3.

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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)

Claims (6)

  1. Tonagglomerat, ausgewählt aus:
    (1) einem Cogranulatagglomerat eines gewebeerweichenden Tons und eines weißfärbenden teilchenförmigen Materials, wobei das Cogranulatagglomerat 30 bis 60 Gew.-% des weißfärbenden teilchenförmigen Materials umfaßt, und
    (2) einem beschichteten Agglomerat mit einem gewebeerweichenden Ton und weißfärbendem teilchenförmigen Material, wobei das weißfärbende Material als ein Überzug auf einem Agglomerat des genannten gewebeerweichenden Tons vorliegt, das beschichtete Agglomerat 10 bis 40 Gew.-% des teilchenförmigen Materials umfaßt und
    wobei das weißfärbende teilchenförmige Material eine durchschnittliche Teilchengröße von weniger als 20 »m, eine Schüttdichte von weniger als 400 g/l und einen Reflexionswert (R unendlich 460) von mehr als 85 aufweist.
  2. Tonagglomerat nach Anspruch 1, wobei das Agglomerat einen R unendlich 460-Wert von größer als 75 aufweist.
  3. Agglomerat nach Anspruch 1 oder Anspruch 2, wobei die Schüttdichte des weißfärbenden teilchenförmigen Materials weniger als 250 g/l beträgt.
  4. Agglomerat nach einem der vorhergehenden Ansprüche, wobei die durchschnittliche Teilchengröße des teilchenförmigen Materials weniger als 15 »m beträgt.
  5. Agglomerat nach einem der vorhergehenden Ansprüche, wobei die durchschnittliche Teilchengröße des teilchenförmigen Materials weniger als 10 »m beträgt.
  6. Reinigungsmittelzusammensetzung mit 5 bis 20 Gew.-% eines Agglomerats nach einem der vorhergehenden Ansprüche.
EP90302125A 1989-03-02 1990-02-28 Agglomerate zum Mischen mit Reinigungspulvern Expired - Lifetime EP0385748B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB898904750A GB8904750D0 (en) 1989-03-02 1989-03-02 Agglomerates for addition to detergent powders
GB8904750 1989-03-02

Publications (3)

Publication Number Publication Date
EP0385748A2 EP0385748A2 (de) 1990-09-05
EP0385748A3 EP0385748A3 (de) 1991-06-05
EP0385748B1 true EP0385748B1 (de) 1995-05-17

Family

ID=10652583

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90302125A Expired - Lifetime EP0385748B1 (de) 1989-03-02 1990-02-28 Agglomerate zum Mischen mit Reinigungspulvern

Country Status (9)

Country Link
EP (1) EP0385748B1 (de)
JP (1) JPH07122073B2 (de)
KR (1) KR950005383B1 (de)
AU (1) AU628136B2 (de)
BR (1) BR9000991A (de)
DE (1) DE69019399T2 (de)
ES (1) ES2074534T3 (de)
GB (1) GB8904750D0 (de)
ZA (1) ZA901608B (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE59309201D1 (de) * 1992-07-17 1999-01-21 Benckiser Nv Maschinenschonendes Geschirrspülmittel
DE4306665A1 (de) * 1993-03-03 1994-09-08 Sued Chemie Ag Waschmittelzusatz für gewebeweichmachende Waschmittel
EP0627484A1 (de) * 1993-06-02 1994-12-07 The Procter & Gamble Company Mit feinkörnigem Material zu beschichtende Tonagglomerate
GB2348884A (en) * 1999-04-13 2000-10-18 Procter & Gamble Light reflecting particles
BRPI0401766A (pt) * 2004-05-17 2006-08-01 Bentonit Uniao Nordeste Sa processo para revestimento de pós granulados secos, produto detergente e amaciante

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4166039A (en) * 1973-10-15 1979-08-28 The Proctor & Gamble Company Detergent composition and process
DE3311568C2 (de) * 1982-04-08 1994-10-20 Colgate Palmolive Co Teilchenförmiges und weichmachendes Grobwaschmittel, Verfahren zu dessen Herstellung und als Zusatz für Grobwaschmittel geeignetes Bentonit-Agglomerat
JPS60262895A (ja) * 1984-06-11 1985-12-26 ライオン株式会社 粒状洗剤の製造方法
GB8711423D0 (en) * 1987-05-14 1987-06-17 Unilever Plc Detergent composition
JPH07122153B2 (ja) * 1987-06-02 1995-12-25 第一工業製薬株式会社 粉体洗浄剤組成物
GB8818277D0 (en) * 1988-08-01 1988-09-07 Ecc Int Ltd Coated clay granules

Also Published As

Publication number Publication date
ES2074534T3 (es) 1995-09-16
ZA901608B (en) 1991-11-27
EP0385748A3 (de) 1991-06-05
DE69019399D1 (de) 1995-06-22
AU5054290A (en) 1990-09-06
EP0385748A2 (de) 1990-09-05
AU628136B2 (en) 1992-09-10
BR9000991A (pt) 1991-02-19
DE69019399T2 (de) 1995-09-21
KR900014575A (ko) 1990-10-24
JPH07122073B2 (ja) 1995-12-25
GB8904750D0 (en) 1989-04-12
JPH02279797A (ja) 1990-11-15
KR950005383B1 (ko) 1995-05-23

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