EP0030859A2 - Procédé de préparation de compositions détergentes - Google Patents

Procédé de préparation de compositions détergentes Download PDF

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Publication number
EP0030859A2
EP0030859A2 EP80304507A EP80304507A EP0030859A2 EP 0030859 A2 EP0030859 A2 EP 0030859A2 EP 80304507 A EP80304507 A EP 80304507A EP 80304507 A EP80304507 A EP 80304507A EP 0030859 A2 EP0030859 A2 EP 0030859A2
Authority
EP
European Patent Office
Prior art keywords
spray
weight
dried
detergent
secondary alkane
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.)
Granted
Application number
EP80304507A
Other languages
German (de)
English (en)
Other versions
EP0030859B1 (fr
EP0030859A3 (en
Inventor
Keith Clarke
Richard Llewellyn Davies
Derek Nicholls
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
Original Assignee
Unilever PLC
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 filed Critical Unilever PLC
Publication of EP0030859A2 publication Critical patent/EP0030859A2/fr
Publication of EP0030859A3 publication Critical patent/EP0030859A3/en
Application granted granted Critical
Publication of EP0030859B1 publication Critical patent/EP0030859B1/fr
Expired 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
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • 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
    • C11D3/06—Phosphates, including polyphosphates
    • 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

Definitions

  • This invention relates to spray-dried detergent powder and to a process for its production.
  • the detergent active material in spray-dried detergent powder is sodium alkylbenzene sulphonate.
  • manufacturers of detergent powders continue to investigate the viability of alternative detergent active materials and have persisted in research and development despite the fact that in very few compositions is it possible to make a simple substitution for one detergent active compound for another and retain the same essential properties. This latter statement applies both to the processing of the composition and to the properties to be expected from it.
  • One detergent active compound which we have investigated is sodium secondary alkane sulphonate, but when we have simply substituted it for sodium alkylbenzene sulphonate in a standard formulation which also contained nonionic surfactant and soap we have found that the resultant spray-dried powder cakes badly and is discoloured. Indeed we have come to associate the presence of nonionic surfactant together with sodium secondary alkane sulphonate with discolouration of the powder during spray-drying.
  • the invention provides a process for the production of a soap-free spray-dried detergent powder which comprises forming an aqueous crutcher slurry comprising one or more secondary alkane sulphonates containing from 13 to 19 carbon atoms, optionally a small amount of a nonionic surfactant, from 10-45% by weight, based on the weight of the spray-dried detergent powder of hydrated sodium tripolyphosphate having a number average crystal size of less than 25 microns and from 4-14% by weight of sodium silicate having a molar ratio S i 02:N a 20 of from 4:1 to 1:1, the process comprising adjusting the temperature of the slurry to from 85 to 95°C and spray-drying it.
  • the number average crystal size of the sodium tripolyphosphate is no more than 10 microns.
  • the detergent composition will be packed in a package manufactured from a substantially vapour-impermeable material, for example a material laminated or coated with polyethylene or with wax.
  • the secondary alkane sulphonate may be present in an amount of from 4 to 30%, preferably for economic reasons, from 7 to 25%, and most preferably from 10 to 14% by weight of the composition.
  • the invention relates to spray-dried detergent powders containing only small amounts of nonionic surfactant, typically less than 3.5%.
  • nonionic surfactant typically less than 3.5%.
  • the anti-foams may be incorporated in the slurry and spray-dried with the other crutcher slurry components, or they may be added to the spray-dried powder by a post-dosing technique.
  • the non-soap anti-foam can be any material not based on soap which exhibits the property of reducing foam produced by anionic surfactants.
  • Typical of non-soap anti-foams are alkyl phosphoric acids and their salts, both used alone and used in conjunction with waxes or hydrophobic oils such as mineral and vegetable oils. Silicone anti-foams and derivatives of nitrogen-containing heterocyclic compounds such as s-triazine may also be used.
  • non-soap anti-foams of this invention may be present in the compositions in amounts from 0.05%, which would be the minimum amount which could possibly be effective, to 5%, which would be the practical maximum having regard to the extreme efficacy of the majority of non-soap anti-foams, to their expense and to the necessity for keeping as much room in the composition as possible for other components.
  • alkyl phosphoric acids which may be used, optionally in sodium, potassium, calcium or magnesium salt form, have the following general formula: where A is -OH or R 2 O(EO) m - , R 1 and R 2 are the same or different C 12 -C 24 , preferably C 16 -C 22 , straight or branched chain, saturated or unsaturated alkyl groups, especially C16-C18 linear saturated groups and m and n are the same or different and are 0 or an integer of from 1 to 6.
  • A is -OH and n is O, so that the compounds are the monoalkyl phosphoric acids, preferably with linear alkyl groups.
  • the alkyl phosphoric acids are commonly mixtures of both mono- and di-alkyl phosphoric acids, with a range of alkyl chain lengths.
  • Predominantly monoalkyl phosphoric acids are usually made by phosphorylation of alcohols or ethoxylated alcohols, when n or m is 1 to 6, using a polyphosphoric acid.
  • Phosphorylation may alternatively be accomplished using phosphorus pentoxide, in which case the mixed mono- and di-alkyl phosphoric acids are produced. Under optimum reaction conditions only small quantities of unreacted materials or by-products are produced, and the reaction products can advantageously be used directly in the detergent compositions.
  • the wax may be of synthetic, mineral, vegetable or animal origin.
  • the waxes should normally melt at a temperature between about 20°C and about 120°C, preferably not more than about 90°C and especially in the range of about 30°C to about 70°C, i.e. lower than the maximum intended wash temperatures for the detergent compositions.
  • waxes having melting points above the maximum intended wash temperatures they should be adequately dispersed in the wash liquor by suitable incorporation in the original detergent compositions.
  • the preferred waxes are of mineral origin, especially those derived from petroleum, including microcrystalline and oxidised microcrystalline petroleum waxes, petroleum jelly ("Vaseline”) and paraffin waxes.
  • Petroleum jelly is correctly a semi-solid wax, usually having a pour point about 40-45°C, but is for convenience here grouped with other solid waxes.
  • Synthetic waxes such as Fischer-Tropsch and oxidised Fischer-Tropsch waxes, or Montan waxes, or natural waxes such as beeswax, candelilla and carnauba waxes may be used if desired. Any of the waxes described may be used alone or in admixture with other waxes.
  • the waxes should be readily dispersible in the detergent liquor but not soluble therein and, preferably, they should not have very high saponification values, e.g. not in excess of about 100. It is advantageous to include emulsifying or stabilising agents for the waxes in the detergent compositions.
  • oils which may be used if desired are vegetable oils such as sesame oil, cottonseed oil, corn oil, sweet almond oil, olive oil, wheat germ oil, rice bran oil, or peanut oil, or animal oils such as lanolin, neat's foot oil, bone oil, sperm oil or cod liver oil. Any such oils used should of course not be highly coloured, of strong odour or otherwise unacceptable for use in a detergent composition.
  • compositions of this invention contain from 10-45% by weight of hydrated sodium tripolyphosphate and that the number average crystal size of this material is less than 25 microns, preferably less than 10 microns.
  • compositions containing lower amounts of sodium tripolyphosphate, or in which the average crystal size is greater than 25 microns, are prepared they are found to have a soft appearance and to have unsatisfactory flow properties in that there is an unacceptably high "threshhold" before they begin to flow at all.
  • compositions containing lesser amounts of silicate than 4-14% have also been found to cake badly.
  • a discovery we have made which is relevant to the processing aspect of this invention is that by correct choice of the appropriate composition parameters specified above, it is possible to reduce the water content of the crutcher slurry to as little as 35% by weight, typically 35-40% by weight. Lower amounts of water have resulted in a slurry which is not easily atomised, but in view of the fact that the normal slurry water content would be 40-45 % by weight, reduction of up to 25% in the amount of water which has to be evaporated during spray-drying represents a very substantial saving.
  • a second discovery which is also relevant to the processing aspect of this invention, is that the higher the temperature of the crutcher slurry, the more free-flowing the spray-dried powder produced. Consequently, we specify a temperature of from 85 to 95°C, preferably 90 to 95°C, for the slurry.
  • sodium tripolyphosphate is present in the slurry it is essential to ensure that the temperature does not rise above 95°C, since above that temperature hydration is prevented and hydrolysis is accelerated, possibly resulting in powders which flow poorly and are prone to caking.
  • Sodium ortho- and pyrophosphates are amongst several suitable detergency builders which are well known and are suitable for use with tripolyphosphates.
  • detergency builders which may be mentioned by way of example are alkali metal carbonates, especially sodium carbonate, alkyl methyl polyphosphonates, e.g.
  • sodium ethane-1-hydroxy-1,1-dipHosphonate alkyl metal amine carboxylates such as sodium nitrolotriacetate and sodium ethylenediamine tetraacetate
  • alkali metal ether carboxylates such as sodium oxydiacetate, sodium carboxymethyloxysuccinate, sodium carboxymethyloxy- malonate and homologues thereof
  • alkali metal citrates alkali metal mellitates and salts of polymeric carboxylic acids, such as sodium polymaleate, copolyethylenemaleate, polyitaconate and polyacrylate.
  • sodium carbonate is used as a detergency builder, it is advantageous to have present some calcium carbonate having a surface area of at least about 10m /g, as described in UK Patent 1,437,950.
  • detergency builder which can be used, either alone or in admixture with other builders, is a cation exchange material, especially a sodium aluminosilicate such as described in UK Patent 1,429,143 or in Netherlands Patent Application 7403381.
  • Preferred materials of this type have the formula: and may be amorphous or crystalline, with some bound water usually in an amount of about 10-30% depending on the drying conditions used.
  • Such sodium aluminosilicate materials should, of course, be very finely divided so as to minimise-deposition on the fabrics during washing.
  • the amount of the detergency builder which is used is normally from about 10% up to about 80% by weight of the composition, preferably about 10% to about 60%, and the ratio by weight of the detergency builders to the detergent active compounds which are used is generally from about 10:1 to about 1:5 parts by weight.
  • the detergent compositions of the invention may also include any of the conventional optional additives in the amounts usually employed in detergent compositions.
  • these additives include powder flow aids such as finely divided silicas and aluminosilicates, antiredeposition agents such as sodium carboxymethylcellulose and the cellulose ethers, oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, per-acid bleaches and precursors thereof such as tetraacetyl- ethylenediamine, chlorine-releasing bleaching agents such as trichloroisocyanuric acid and alkali metal salts of dichloroisocyanuric acid, fabric softening agents such as clays of the smectite and illite types, anti-ashing aids, starches, slurry stabilisers such as copolyethylenemaleic anhydride and copolyvinylmethylether maleic anhydride, usually in salt form, slurry hydrotropes such as sodium toluene sulphonate, inorganic salt
  • Three detergent powders A,B and C were prepared by slurry making, spray-drying and dry-dosing techniques and under the spray-drying conditions described below. Their formulations were as follows:
  • Powder C which contains a relatively large amount of nonionic surfactant and which is consequently not within the scope of this invention was yellow in colour.
  • Powder A which is free of nonionic surfactant, but which was spray-dried at a slurry temperature of only 80°C was not discoloured but had an unsatisfactory dynamic flow rate.
  • Powder B which is in accordance with the invention was white and had satisfactory dynamic flow rate and caking characteristics.

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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)
EP80304507A 1979-12-14 1980-12-12 Procédé de préparation de compositions détergentes Expired EP0030859B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB7943219 1979-12-14
GB7943219 1979-12-14

Publications (3)

Publication Number Publication Date
EP0030859A2 true EP0030859A2 (fr) 1981-06-24
EP0030859A3 EP0030859A3 (en) 1982-01-27
EP0030859B1 EP0030859B1 (fr) 1984-10-31

Family

ID=10509860

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80304507A Expired EP0030859B1 (fr) 1979-12-14 1980-12-12 Procédé de préparation de compositions détergentes

Country Status (4)

Country Link
EP (1) EP0030859B1 (fr)
JP (1) JPS5698299A (fr)
DE (1) DE3069571D1 (fr)
ZA (1) ZA807664B (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0054436A1 (fr) * 1980-12-17 1982-06-23 Unilever Plc Composition détergente à mousse contrôlée
EP0236270A3 (fr) * 1986-02-28 1989-06-28 Ciba-Geigy Ag Procédé de préparation de corps contenant une substance active et leur utilisation comme "speckles"
WO1998031775A1 (fr) * 1997-01-21 1998-07-23 Clariant Gmbh Sulfonate d'alcane secondaire granulaire
WO2009112187A1 (fr) * 2008-03-11 2009-09-17 Clariant International Ltd Procédé pour produire des sels de métal alcalino-terreux solides d’acides paraffine-sulfoniques secondaires
WO2012084150A1 (fr) * 2010-12-22 2012-06-28 Clariant International Ltd Compositions contenant un sulfonate de paraffine secondaire et un alcoxylat d'alcool
WO2012084151A1 (fr) * 2010-12-22 2012-06-28 Clariant International Ltd Compositions contenant un sulfonate de paraffine secondaire et un alcoxylat d'alcool
WO2012084149A1 (fr) * 2010-12-22 2012-06-28 Clariant International Ltd Compositions contenant un sulfonate de paraffine secondaire et une tétrahydroxypropyl éthylène diamine

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5335081B1 (fr) * 1971-06-30 1978-09-25
US3959165A (en) * 1972-09-15 1976-05-25 Colgate-Palmolive Company Biodegradable, non-polluting, heavy duty synthetic organic detergent composition
DE2423391C2 (de) * 1974-05-14 1983-08-04 Hoechst Ag, 6230 Frankfurt Waschmittel

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0054436A1 (fr) * 1980-12-17 1982-06-23 Unilever Plc Composition détergente à mousse contrôlée
EP0236270A3 (fr) * 1986-02-28 1989-06-28 Ciba-Geigy Ag Procédé de préparation de corps contenant une substance active et leur utilisation comme "speckles"
WO1998031775A1 (fr) * 1997-01-21 1998-07-23 Clariant Gmbh Sulfonate d'alcane secondaire granulaire
WO2009112187A1 (fr) * 2008-03-11 2009-09-17 Clariant International Ltd Procédé pour produire des sels de métal alcalino-terreux solides d’acides paraffine-sulfoniques secondaires
US8426635B2 (en) 2008-03-11 2013-04-23 Clariant Finance (Bvi) Limited Process for preparing solid alkaline earth metal salts of secondary paraffinsulphonic acids
WO2012084150A1 (fr) * 2010-12-22 2012-06-28 Clariant International Ltd Compositions contenant un sulfonate de paraffine secondaire et un alcoxylat d'alcool
WO2012084151A1 (fr) * 2010-12-22 2012-06-28 Clariant International Ltd Compositions contenant un sulfonate de paraffine secondaire et un alcoxylat d'alcool
WO2012084149A1 (fr) * 2010-12-22 2012-06-28 Clariant International Ltd Compositions contenant un sulfonate de paraffine secondaire et une tétrahydroxypropyl éthylène diamine
US8987179B2 (en) 2010-12-22 2015-03-24 Weylchem Switzerland Ag Compositions containing secondary paraffin sulfonate and alcohol alkoxylate

Also Published As

Publication number Publication date
ZA807664B (en) 1982-07-28
EP0030859B1 (fr) 1984-10-31
EP0030859A3 (en) 1982-01-27
JPS6110520B2 (fr) 1986-03-29
DE3069571D1 (en) 1984-12-06
JPS5698299A (en) 1981-08-07

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