EP0242141A2 - Poudres détergentes et leur procédé de préparation - Google Patents

Poudres détergentes et leur procédé de préparation Download PDF

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Publication number
EP0242141A2
EP0242141A2 EP87303159A EP87303159A EP0242141A2 EP 0242141 A2 EP0242141 A2 EP 0242141A2 EP 87303159 A EP87303159 A EP 87303159A EP 87303159 A EP87303159 A EP 87303159A EP 0242141 A2 EP0242141 A2 EP 0242141A2
Authority
EP
European Patent Office
Prior art keywords
weight
powder
spray
detergent
dried
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.)
Withdrawn
Application number
EP87303159A
Other languages
German (de)
English (en)
Other versions
EP0242141A3 (fr
Inventor
Seeng Djiang Liem
Frederik Alain Veer
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
Publication of EP0242141A2 publication Critical patent/EP0242141A2/fr
Publication of EP0242141A3 publication Critical patent/EP0242141A3/fr
Withdrawn legal-status Critical Current

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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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C11D7/14—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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof

Definitions

  • the present invention relates to a process for preparing low or zero-phosphorus detergent powders containing alkalimetal aluminosilicate as the sole or principal builder, and also containing appreciable levels of alkali metal silicate.
  • the process of the invention combines the techniques of spray-drying and post-dosing.
  • Alkali metal aluminosilicates both crystalline (zeolites) and amorphous, are effective detergency builders which can be used to replace sodium tripolyphosphate (STP) in detergent powders, but they do not possess an ability comparable to that of STP to contribute to the structure of a spray-dried powder.
  • Alkali metal silicates are frequently included in detergent powders as structurants, to reduce washing machine corrosion and to increase alkalinity. It is well known, however, that if aluminosilicate and silicate are together in a detergent slurry they can interact unfavourably: agglomeration of the aluminosilicate occurs to give powders containing large particles which are slow to disperse in the wash liquor, giving reduced washing performance.
  • EP 10 247B (Henkel KGaA) discloses a solution to this problem: silicate is omitted from the slurry, and instead is admixed subsequently with the spray-dried powder.
  • the slurry contains aluminosilicate, surfactant and certain organic sequestrant builder materials, while the silicate is postdosed in the form of a powder having a Na2O:SiO2 mole ratio of 2.0 to 2.2, a water content of 15-23% by weight and a high water solubility.
  • Other ingredients unsuitable for spray-drying, for example, certain nonionic surfactants, may also be postdosed.
  • Powders made by this process exhibit improved washing performance, since the aluminosilicate is carried through into the powder, and into the wash, in the form of small particles.
  • the physical properties of these powders tend, however, to be poor and the powder strength low.
  • powders of greatly improved physical properties and attractive appearance may be produced by this method if there is included in the slurry an additional powder structurant which comprises succinic acid or a wholly or partially neutralised salt thereof.
  • the present invention provides a process for the production of a detergent powder having a phosphorus content of not more than 2.5% by weight and comprising one or more anionic and/or nonionic detergent-active compounds, from 10 to 60% by weight of crystalline or amorphous sodium aluminosilicate builder, from 1 to 10% by weight of water-soluble sodium silicate and optionally other conventional ingredients, the process comprising the steps of
  • the invention further provides a detergent powder having a phosphorus content of less than 2.5% by weight and comprising one or more anionic and/or nonionic detergent-active compounds, from 10 to 60% by weight of crystalline or amorphous sodium aluminosilicate, from 1 to 10% by weight of water-soluble sodium silicate, from 0.5 to 10% by weight of succinic acid or a wholly or partially neutralised salt thereof, and optionally other conventional ingredients, the powder being prepared by the process defined in the previous paragraph.
  • the detergent powders of the invention preferably have a phosphorus content of less than 1% by weight, and zero-P powders are especially preferred.
  • One class of preferred powders in accordance with the invention is constituted by high bulk density powders having bulk densities of at least 400 g/litre and agglomerate strengths (as hereinafter defined) of at least 7 N/cm2 prior to the addition of the postdosed ingredients.
  • the process of the invention is characterised by a combination of two features: first, use of a reduced level of silicate in the slurry, or none at all, compensated by postdosing solid sodium silicate having especially good dissolution characteristics; and secondly, inclusion of succinic acid or a salt thereof as a structurant in the slurry to make up for the loss of the structuring power of silicate in the slurry.
  • Silicate processed via the slurry may of course be the usual aqueous solution (waterglass) form.
  • the postdosed silicate which constitutes the whole or the greater part of the total silicate in the powder, is in the form of a particulate solid. As this could be entering the wash liquor without further processing, other than mixing with the spray-dried base powder, it must be carefully selected with respect to its rate of solution characteristics.
  • silicate ratio range excludes neutral silicate (ratio 3.3:1) which is too highly polymerised to give adequate dissolution characteristics, but includes the more alkaline materials up to and including sodium metasilicate (ratio 1:1).
  • the moisture content of the silicate may vary quite widely: for the amorphous alkaline silicates values of 16 to 25% by weight are typical, whereas hydrated metasilicate, with five moles of water of crystallisation per mole, generally has a moisture content of 42-44% by weight.
  • the bulk density of the postdosed silicate is at least 400 g/litre; for the amorphous alkaline silicates a bulk density within the range of from 400 to 900 g/litre is preferred, while the bulk density of metasilicate suitable for use in the invention may be as high as 1000 g/litre.
  • the particulate sodium silicate used in the process of the invention is preferably prepared by spray-drying.
  • Silicate A.1 An especially preferred sodium alkaline silicate (ratio 2:1), prepared by spray-drying under carefully controlled conditions, is commercially available from Joseph Crosfield & Sons Ltd, UK as "Silicate A.1".
  • the rate of solution of this material is such that at 20°C at least 90% by weight dissolves in distilled water within 1 minute and at least 99% by weight dissolves within 3 minutes.
  • the moisture content of "Silicate A.1" is in the 18-21% by weight range.
  • succinic acid or a wholly or partially neutralised salt thereof is also incorporated in the powder by way of the slurry, in an amount of from 0.5 to 10% by weight, preferably an amount of 0.5 to 6% by weight, based on the final powder.
  • Succinate structurants may be added to the slurry in acid, partially neutralised or wholly neutralised form: neutralisation will generally be completed in the slurry.
  • Our copending application of even date (Case C.3112) describes and claims the use of succinic acid and sodium carbonate in detergent slurries to form sodium sesquicarbonate in situ as a structurant.
  • succinic acid may be incorporated as Sokalan (Trade Mark) DCS, a mixture of succinic acid (20-25% by weight), adipic acid (30-35% by weight) and glutaric acid (40-50% by weight) ex BASF.
  • an anionic polymer may also be included in the slurry as an additional structurant, as described and claimed in our copending Application of even date claiming the priority of British Patent Applications Nos. 86 08291 and 86 09042 filed on 4 April and 14 April 1986.
  • Polymeric structurants are advantageously used in amounts of from 0.2 to 10% by weight, and the succinate structurant is then preferably used in an amount of from 0.5 to 3% by weight.
  • Preferred polymeric powder structurants are water-soluble anionic polymers, especially polymeric polycarboxylates and their derivatives. Especially preferred polymers are homopolymers and copolymers of acrylic acid and its salts.
  • Some polymers are also beneficial in respects other than structuring; for example, acrylic polymers have calcium binding building properties. Some polymers may provide anti-ashing or antiredeposition benefits. The use of polymeric structurants that also give performance benefits of this type is especially preferred.
  • Suitable polymers include the following, the list not being exhaustive: salts of polyacrylic acid, for example, Versicol (Trade Mark) E5, E7 and E9 ex Allied Colloids, average molecular weights 3500, 27 000 and 70 000 respectively; Narlex (Trade Mark) LD 30 and 34 ex National Adhesives and Resins Ltd, average molecular weights 14 000 and 72 000 respectively; and Sokalan (Trade Mark) PA 50 and PA 110S ex BASF, average molecular weights 30 000 and 250 000 respectively; acrylic acid/maleic anhydride copolymers, for example, Sokalan (Trade Mark) CP5 and CP7 ex BASF, average molecular weights 70 000 and 50 000 respectively; and acrylic phosphinates, for example, the DKW range ex National Adhesives and Resins Ltd or the Belsperse range ex Ciba-Geigy AG, as disclosed in EP 182 411A (Unilever); ethylene/maleic anhydride copolymers, for example
  • the first three classes of polymer are especially preferred.
  • Mixtures of two or more polymeric structurants may if desired be used in the process of the invention.
  • Detergent powders prepared in accordance with the invention exhibit better physical properties than powders containing no succinate structurant: in particular, the agglomerate strength of the spray-dried base powder is superior.
  • the agglomerate strength is defined as the pressure that has to be exerted on a sample of powder to compress it to a bed porosity of 0.4. The latter value has been selected since it is known to be the bed porosity of densely packed granular solids, including detergent powders: to achieve bed porosities below 0.4 any agglomerates in a powder sample have to be broken down into the primary particles of which they are composed, these primary particles corresponding in size to the droplets formed when the detergent slurry was atomised in the spray-drying tower.
  • the agglomerate strength is a measure of the resistance of the agglomerates in a powder, on compression, to breakdown into the smaller primary particles.
  • the agglomerate strength is measured as follows. A 0.3 g sample of the 250-500 ⁇ m sieve fraction of the spray-dried base powder is subjected to compression in a compression cell of circular cross-section, having a diameter of 1.3 cm and (hence) a cross-sectional area of 1.33 cm2. The work of compression is measured and plotted against the height of the powder bed in the cell.
  • Bed porosity as a function of bed height can be calculated from the bulk density of the powder bed (calculated from the weight of the powder sample, its height and the cross-sectional area of the compression cell), the true density of the material (solids density) and the powder porosity, by means of the following equation:
  • the particle porosity must be determined by air permeametry, a standard technique, using the equation derived by Carman and Kozeny in J. Society of Chemistry and Industry (London) 57 , 225 T (1938).
  • Agglomerate strength values which refer to the spray-dried base powder obtained from step (i) before addition of the postdosed ingredients in step (ii), depend on bulk density as well as on the formulation of the slurry, and for powders having bulk densities of 400 g/litre or above will typically be within the range of from 7 to 30 N/cm2 for powders in accordance with the invention and from 4 to 6 N/cm2 for powders containing no succinate structurant.
  • the invention will normally give powders having agglomerate strengths in the 1 to 15 N/cm2 range, as compared with less than 1 N/cm2 for similar powders without succinate structurant.
  • Powders of intermediate bulk density 250-400 g/litre
  • the detergent powders prepared in accordance with the invention contain alkali metal aluminosilicate as the sole or principal builder, in an amount of from 10 to 60% by weight based on the final powder.
  • the alkali metal (preferably sodium) aluminosilicate used in the composition of the invention may be either crystalline or amorphous or mixtures thereof, and has the general formula 0.8-1.5 Na2O.Al2O3.0.8-6 SiO2.
  • the preferred sodium aluminosilicates contain 1.5-3.5 SiO2 units (in the formula above) and have a particle size of not more than about 100 ⁇ m, preferably not more than about 20 ⁇ m and more preferably not more than about 10 ⁇ m. Both the amorphous and crystalline sodium aluminosilicates can be made readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
  • Suitable crystalline sodium sluminosilicate ion-exchange detergency builders are described, for example, in GB 1 473 210 (Henkel) and GB 1 429 143 (Procter & Gamble).
  • the preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof.
  • the detergent powders prepared in accordance with the invention are preferably free of phosphate builders.
  • Other inorganic or organic non-phosphate builders for example, sodium carbonate or sodium nitrilotriacetate, may also be present, as may other inorganic salts such as sodium sulphate.
  • Phosphate builders may, however, be present in limited amounts, provided that the upper limit of 2.5% P is not exceeded, but, as indicated previously, the invention is of especial applicability to zero-P powders.
  • the detergent powders prepared by the process of the present invention also contain one or more anionic and/or nonionic surfactants.
  • Anionic surfactants are well known to those skilled in the detergents art. Examples include alkylbenzene sulphonates, particularly sodium linear alkylbenzene sulphonates having an average chain length of about C12; primary and secondary alcohol sulphates, particularly sodium C12-C15 primary alcohol sulphates; olefin sulphonates; alkane sulphonates; and fatty acid ester sulphonates.
  • Nonionic surfactants that may be used in the process and compositions of the invention include the primary and secondary alcohol ethoxylates, especially the C12-C15 primary and secondary alcohols ethoxylated with an average of from 3 to 20 moles of ethylene oxide per mole of alcohol.
  • soaps of fatty acids are preferably sodium soaps derived from naturally occurring fatty acids, for example the fatty acids from coconut oil, beef tallow, or sunflower oil.
  • Anionic surfactants both soap and non-soap, will generally be incorporated via the slurry, while nonionic surfactants may either be incorporated in the slurry or postdosed.
  • the total amount of detergent-active material (surfactant), excluding soap, in the detergent powders of the invention is preferably within the range of from 5 to 30% by weight.
  • the preferred range is from 5 to 20% by weight, with a weight ratio of anionic surfactant to nonionic surfactant not exceeding 10:1, and more preferably not exceeding 6:1.
  • the level of sodium silicate in the slurry preferably does not exceed 1% by weight: agglomeration problems, leading to unacceptable levels of insoluble particles in the wash liquor, may be encountered at higher levels. Powders with higher ratios of anionic surfactant to nonionic surfactant can tolerate higher levels of silicate in the slurry.
  • Detergent compositions in accordance with the present invention may also contain any other of the ingredients conventionally present, notably antiredeposition agents; antiincrustation agents; fluorescers; enzymes; bleaches, bleach precursors and bleach stabilisers; lather suppressors; perfumes; and dyes. These may be added to the aqueous slurry or post-dosed into the spray-dried powder, either together with the silicate or separately, according to their known suitability for undergoing spray-drying processes.
  • Powders (1) to (6) are in accordance with the invention while (A) is a comparative powder containing no succinate structurant. Powder (2) additionally contains a polymeric structurant.
  • the high bulk density powders (1), (2) and (3) have agglomerate strengths within the range from 7 to 30 N/cm2, while the value for the comparative powder (A) is only 6 N/cm2.
  • the lower bulk density powders (4), (5) and (6) have agglomerate strengths within the preferred range (1 to 15 N/cm2) for powders of that bulk density.

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
EP87303159A 1986-04-14 1987-04-10 Poudres détergentes et leur procédé de préparation Withdrawn EP0242141A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8609043 1986-04-14
GB868609043A GB8609043D0 (en) 1986-04-14 1986-04-14 Detergent powders

Publications (2)

Publication Number Publication Date
EP0242141A2 true EP0242141A2 (fr) 1987-10-21
EP0242141A3 EP0242141A3 (fr) 1988-11-02

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ID=10596149

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87303159A Withdrawn EP0242141A3 (fr) 1986-04-14 1987-04-10 Poudres détergentes et leur procédé de préparation

Country Status (8)

Country Link
EP (1) EP0242141A3 (fr)
JP (1) JPS62243695A (fr)
KR (1) KR870010174A (fr)
AU (1) AU572418B2 (fr)
BR (1) BR8701757A (fr)
GB (1) GB8609043D0 (fr)
TR (1) TR23366A (fr)
ZA (1) ZA872674B (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0340013A2 (fr) * 1988-04-29 1989-11-02 Unilever Plc Compositions détergentes et procédé pour leur préparation
US5151208A (en) * 1986-04-14 1992-09-29 Lever Brothers Company, Division Of Conopco, Inc. Detergent powders and process for their preparation
WO1997024424A1 (fr) * 1995-12-28 1997-07-10 Rhone-Poulenc Surfactants & Specialties, L.P. Procedes pour produire des compositions solides de tensioactifs se dissolvant plus lentement
EP0639639B1 (fr) * 1993-08-17 1999-12-15 The Procter & Gamble Company Compositions détergentes contenant des percarbonates comme agents de blanchiment
US6534474B1 (en) 1998-06-04 2003-03-18 Kao Corporation Surfactant composition
WO2011092325A3 (fr) * 2010-01-29 2011-09-29 Ecolife B.V. Composition pour la prévention ou l'élimination de dépôts de sels insolubles

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0384100A (ja) * 1989-08-28 1991-04-09 Lion Corp 高嵩密度洗剤組成物の製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0001310A1 (fr) * 1977-09-26 1979-04-04 THE PROCTER & GAMBLE COMPANY Composition détergente à faible teneur en phosphate pour le lavage de textiles
EP0010247A1 (fr) * 1978-10-12 1980-04-30 Henkel Kommanditgesellschaft auf Aktien Produit pour le lavage sans phosphates et procédé pour sa fabrication
EP0061295A1 (fr) * 1981-03-23 1982-09-29 Unilever Plc Procédé de préparation de compositions détergentes à faible teneur en silicats
EP0221777A2 (fr) * 1985-11-01 1987-05-13 Unilever Plc Compositions détergentes

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8609044D0 (en) * 1986-04-14 1986-05-21 Unilever Plc Detergent powders

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0001310A1 (fr) * 1977-09-26 1979-04-04 THE PROCTER & GAMBLE COMPANY Composition détergente à faible teneur en phosphate pour le lavage de textiles
EP0010247A1 (fr) * 1978-10-12 1980-04-30 Henkel Kommanditgesellschaft auf Aktien Produit pour le lavage sans phosphates et procédé pour sa fabrication
EP0061295A1 (fr) * 1981-03-23 1982-09-29 Unilever Plc Procédé de préparation de compositions détergentes à faible teneur en silicats
EP0221777A2 (fr) * 1985-11-01 1987-05-13 Unilever Plc Compositions détergentes

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5151208A (en) * 1986-04-14 1992-09-29 Lever Brothers Company, Division Of Conopco, Inc. Detergent powders and process for their preparation
EP0340013A2 (fr) * 1988-04-29 1989-11-02 Unilever Plc Compositions détergentes et procédé pour leur préparation
EP0340013A3 (fr) * 1988-04-29 1991-05-29 Unilever Plc Compositions détergentes et procédé pour leur préparation
EP0639639B1 (fr) * 1993-08-17 1999-12-15 The Procter & Gamble Company Compositions détergentes contenant des percarbonates comme agents de blanchiment
WO1997024424A1 (fr) * 1995-12-28 1997-07-10 Rhone-Poulenc Surfactants & Specialties, L.P. Procedes pour produire des compositions solides de tensioactifs se dissolvant plus lentement
US6534474B1 (en) 1998-06-04 2003-03-18 Kao Corporation Surfactant composition
WO2011092325A3 (fr) * 2010-01-29 2011-09-29 Ecolife B.V. Composition pour la prévention ou l'élimination de dépôts de sels insolubles
US8415285B2 (en) 2010-01-29 2013-04-09 Ecover Coordination Center N.V. Composition for the prevention or removal of insoluble salt deposits

Also Published As

Publication number Publication date
EP0242141A3 (fr) 1988-11-02
AU7134187A (en) 1987-12-10
BR8701757A (pt) 1988-01-12
TR23366A (tr) 1989-12-28
ZA872674B (en) 1988-12-28
KR870010174A (ko) 1987-11-30
GB8609043D0 (en) 1986-05-21
AU572418B2 (en) 1988-05-05
JPS62243695A (ja) 1987-10-24

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