EP4402232B1 - Verfahren zur herstellung eines sprühgetrockneten waschmittelpartikels - Google Patents

Verfahren zur herstellung eines sprühgetrockneten waschmittelpartikels Download PDF

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Publication number
EP4402232B1
EP4402232B1 EP22785949.3A EP22785949A EP4402232B1 EP 4402232 B1 EP4402232 B1 EP 4402232B1 EP 22785949 A EP22785949 A EP 22785949A EP 4402232 B1 EP4402232 B1 EP 4402232B1
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EP
European Patent Office
Prior art keywords
alkaline earth
spray
earth metal
salt
carboxylic acid
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.)
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EP22785949.3A
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English (en)
French (fr)
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EP4402232A1 (de
Inventor
Abraham Chacko
Girish Kumar
Sharavan KUMAR
Kunal Shankar PAWAR
Nadeem Shaikh
Satyendra Prasad SINGH
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Unilever Global IP Ltd
Unilever IP Holdings BV
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Unilever Global IP Ltd
Unilever IP Holdings BV
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Publication of EP4402232A1 publication Critical patent/EP4402232A1/de
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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
    • 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
    • C11D1/146—Sulfuric 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
    • 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
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
    • 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
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • 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
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile

Definitions

  • the present invention relates to a process for preparing a spray-dried detergent particle. Particularly to spray-dried laundry detergent particle with low pH, low alkalinity and having good particle characteristics.
  • the spray-dried detergent particle is suitable for use as a solid laundry detergent composition or for incorporation into a solid laundry detergent composition.
  • powder detergent compositions have been formulated to provide a pH ranging from 10.5 to 11.5 in a wash solution.
  • a basic pH ensures that the surfactant systems, enzymes, and other ingredients in the composition remain solubilized in the wash water, thereby promoting effective soil release and cleaning performance.
  • Cotton fabric swells at a pH of 9.5 to 10, which allows the surfactant to penetrate deeply into the fibre.
  • a basic pH ensures effective removal of fatty and particulate stains from soiled clothing.
  • the higher pH also has certain disadvantages.
  • Higher pH in the wash solution tends to be harsh on the skin of consumers and are associated with the problem of colour fading of the laundered fabrics.
  • sodium carbonate and sodium silicate contribute to improving the physical properties such as flow and storage behaviours of the spray-dried detergent particle.
  • Past attempts at reducing or eliminating sodium carbonate from the spray-dried detergent particle were not satisfactory as the resultant spray-dried detergent particle were found to have acceptable powder properties only for a short duration that is immediately after spray drying and showed caking on storage.
  • sodium silicate is generally considered a critical ingredient in spray-dried detergent particle as it serves to provide stability and integrity to the detergent particle formed during the spray-drying operation.
  • Sodium silicate also plays a role in the viscosity and flow behaviour of the slurry, a low silicate containing slurry may cause gelation of the slurry and the slurry may be not pumpable.
  • Alkali metal silicate salt Likali metal silicate salt
  • the process according to the first aspect of the present invention includes addition of an alkali metal silicate salt to the aqueous mixture.
  • Alkali metal silicate salt is a common ingredient in the laundry detergent composition.
  • the alkali metal silicate salt preferably has a weight ratio of SiO 2 :M 2 O within the range of 1.6 to 3.3 more preferably 1.6 to 2.4, and most preferably 2.0 to 2.85, wherein M is an alkali metal.
  • the alkali metal silicate salt employed is preferably in the form of an aqueous solution, generally having a solid content from 30 wt.% to 45 wt.% by weight of the aqueous solution.
  • the alkali metal silicate salt may be selected from the group consisting of sodium silicate, potassium silicate, sodium-potassium double silicate or mixtures thereof.
  • the alkali metal silicate salt is water-soluble.
  • the alkali metal silicate salt employed is sodium silicate.
  • the sodium silicate has a weight ratio, SiO 2 :Na 2 O within the range of 1.6 to 3.3 more preferably 1.6 to 2.4, and most preferably 2.0 to 2.85.
  • the amount of alkali metal silicate added to the aqueous mixture is such that the spray-dried detergent particle formed preferably comprises less than 5 wt.% still preferably less than 2 wt.% alkali metal silicate salt, still preferably less than 1 wt.%.
  • the alkaline earth metal compound is preferably selected from a magnesium salt, a calcium salt or mixtures thereof.
  • the alkaline earth metal salt may be preferably selected from calcium sulphate, magnesium sulphate, calcium chloride, magnesium chloride or mixtures thereof.
  • the alkaline earth metal compound is a magnesium salt and still preferably the alkaline earth metal compound/salt is magnesium sulphate.
  • Aqueous mixture :
  • the detersive surfactant is anionic, nonionic or mixtures thereof. More preferably the aqueous mixture includes an anionic surfactant. Suitable anionic detersive surfactant is an alkyl sulphonate surfactant, alkyl sulphate surfactant or mixtures thereof. The anionic surfactant and/or nonionic surfactant may be linear or branched, substituted or unsubstituted.
  • the aqueous mixture preferably includes a detersive surfactant.
  • the detersive surfactant is preferably an anionic surfactant.
  • the detersive anionic surfactant is either pre-neutralized and added into the aqueous mixture or a liquid acid form of the anionic surfactant is added to the aqueous mixture and neutralized in-situ.
  • the acid form of the anionic surfactant may be partly neutralized and thereafter added into the aqueous mixture such that the remaining un-neutralized part of the liquid acid form of the anionic surfactant is neutralized in-situ in the aqueous mixture.
  • Fully pre-neutralized anionic surfactant commercially available in solid form or in the form of paste may also be suitably used.
  • the detersive surfactant is added to the aqueous mixture before addition of the alkaline earth metal compound.
  • the detersive surfactant, especially in the fully pre-neutralized salt form is added to the aqueous mixture after addition of the alkaline earth metal compound/salt or along with the alkaline earth metal compound/salt.
  • the detersive surfactant in the fully neutralized salt form may be added to the base mixture after the formation of the organic carboxylic acid salt of alkaline earth metal.
  • the partly neutralized anionic surfactant is preferably prepared by a neutralization process which involves the step of (i) mixing a liquid acid form of the anionic surfactant and a neutralizing agent to form a partially neutralized solution; preferably the neutralizing agent is an alkali metal hydroxide, wherein the amount of alkali metal hydroxide neutralizing agent is sufficient to react with a portion of liquid acid anionic surfactant precursor to form in-situ anionic surfactant salt.
  • the neutralized anionic surfactant formed by neutralizing the acid form with the alkali metal hydroxide neutralizing agent preferably contributes from 28 parts to 98 parts of the total anionic surfactant by weight present in the spray-dried detergent particle.
  • alkali metal silicate salt to the partly neutralized anionic surfactant in the aqueous mixture, the remaining unreacted acid form of the anionic surfactant reacts with the alkali metal silicate salt to form fully neutralized salt form of the anionic surfactant.
  • a fully neutralized anionic surfactant is added to the aqueous mixture.
  • liquid acid anionic surfactant precursor is reacted with an alkali metal hydroxide to form fully neutralized anionic surfactant salt before addition to the aqueous mixture. More preferably the liquid acid precursor of the anionic surfactant is partly or fully neutralized in-situ. One or more anionic surfactant may be present in the spray-dried detergent particle.
  • the detersive surfactant is present in the aqueous mixture when the alkaline earth metal compound or salt is contacted with the alkali metal silicate salt.
  • the order of addition is to contact the pre-neutralized detersive surfactant or the acid precursor form of the anionic detersive surfactant with water followed by contacting with the alkali metal silicate salt and then adding the alkaline earth metal compound or salt.
  • the part or full neutralization may be carried out in the same vessel by contacting the acid precursor form of the anionic surfactant with an aqueous solution of neutralizing agent (alkali metal hydroxide) to form the neutralized anionic surfactant.
  • the order of addition may be reversed wherein the step involves adding alkaline earth metal compound or salt to the aqueous mixture followed by the alkali metal silicate salt.
  • the detersive surfactant is pH sensitive that is those which undergo hydrolysis at low pH conditions, then it is preferred that the detersive surfactant is added to the aqueous slurry after the pH is raised to 7 or above.
  • the detersive surfactant is primary alkyl sulphate surfactant.
  • PAS has an alkyl chain length of C 8 to C 18 , preferably C 12 to C 14 .
  • the primary alkyl sulphate surfactant is linear or branched, preferably linear.
  • the primary alkyl sulphate surfactant is substituted or unsubstituted.
  • the detersive surfactant is an anionic surfactant.
  • Suitable anionic detersive surfactant includes sulphonate and sulphate surfactant.
  • Suitable sulphonate surfactant include alkyl ester sulphonate, alpha olefin sulphonate, alkyl benzene sulphonate, especially alkyl benzene sulphonate, preferably C 10 to C 13 alkyl benzene sulphonate.
  • a preferred detersive anionic surfactant is linear alkyl benzene sulphonate, where the alkyl chain has 5 to 20 carbon atoms, more preferably the linear alkylbenzene sulphonate surfactant has a C 10 to C 18 alkyl group, still preferably C 10 to C 14 alkyl group.
  • Suitable alkyl benzene sulphonate (LAS) is obtainable, preferably obtained, by sulphonating commercially available linear alkyl benzene (LAB); suitable LAB includes low 2-phenyl LAB, other suitable LAB includes high 2-phenyl LAB, such as those supplied by Sasol under the tradename Hyblene ® .
  • Suitable sulphate surfactant includes alkyl sulphate, preferably C 8 to C 18 alkyl sulphate, or predominantly C 12 to C 18 alkyl sulphate.
  • a preferred sulphate detersive surfactant is alkyl alkoxylated sulphate, preferably alkyl ethoxylated sulphate, preferably a C 8 to C 18 alkyl alkoxylated sulphate, preferably a C 8 to C 18 alkyl ethoxylated sulphate, preferably the alkyl alkoxylated sulphate has an average degree of alkoxylation from 0.5 to 20, preferably from 0.5 to 10, preferably the alkyl alkoxylated sulphate is a C 8 to C 18 alkyl ethoxylated sulphate having an average degree of ethoxylation of from 0.5 to 10, preferably from 0.5 to 5, more preferably from 0.5 to 3 and most preferably from 0.5 to 1.5.
  • alkyl sulphate, alkyl alkoxylated sulphate and alkyl benzene sulphonate may be linear or branched, substituted or un-substituted and may be derived from petrochemical material or biomaterial.
  • suitable anionic detersive surfactant includes soaps, alkyl ether carboxylates.
  • Suitable anionic detersive surfactant may be in salt form, suitable counter-ions include sodium, calcium, magnesium, amino alcohol, and any combinations thereof. A preferred counterion is sodium.
  • Suitable non-ionic detersive surfactant are selected from the group consisting of: C 8 to C 18 alkyl ethoxylates, such as, NEODOL ® non-ionic surfactants from Shell; C 6 to C 12 alkyl phenol alkoxylates wherein preferably the alkoxylate units are ethyleneoxy units, propyleneoxy units or a mixture thereof; C 12 to C 18 alcohol and C 6 to C 12 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as Pluronic ® from BASF; alkyl polysaccharides, preferably alkyl polyglycosides; methyl ester ethoxylates; polyhydroxy fatty acid amides; ether capped poly(oxyalkylated) alcohol surfactants and mixtures thereof.
  • C 8 to C 18 alkyl ethoxylates such as, NEODOL ® non-ionic surfactants from Shell
  • Suitable non-ionic detersive surfactants are alkyl polyglucoside and/or an alkyl alkoxylated alcohol.
  • Suitable non-ionic detersive surfactants include alkyl alkoxylated alcohols, preferably C 8 to C 18 alkyl alkoxylated alcohol, preferably a C 8 to C 18 alkyl ethoxylated alcohol, preferably the alkyl alkoxylated alcohol has an average degree of alkoxylation of from 1 to 50, preferably from 1 to 30, or from 1 to 20, or from 1 to 10, preferably the alkyl alkoxylated alcohol is a C 8 to C 18 alkyl ethoxylated alcohol having an average degree of ethoxylation of from 1 to 10, preferably from 1 to 7, more preferably from 1 to 5 and most preferably from 3 to 7.
  • the alkyl alkoxylated alcohol can be linear or branched and substituted or un-substituted.
  • Suitable nonionic detersive surfactants include secondary alcohol-
  • Zwitterionic surfactant Suitable zwitterionic detersive surfactants include amine oxides and/or betaines.
  • One or more detersive surfactant may be present in the spray-dried detergent particle according to the present invention.
  • the surfactant is preferably those which are thermally stable during processing conditions of a spray-drying tower where typically the inlet air temperature ranges from 250°C to 500°C and those which are chemically stable at the pH conditions of the spray-drying slurry.
  • Non-limiting examples of the anionic surfactant includes the ones mentioned above.
  • the alkali metal silicate salt reacts with the alkaline earth metal compound in an aqueous mixture to form an in-situ intermediate mixture.
  • the intermediate mixture includes one or more compound selected from the group consisting of hydroxide of alkaline earth metal, silicate salt of alkaline earth metal, disilicate salt of alkaline earth metal or mixture thereof.
  • the intermediate mixture includes alkaline earth metal silicate, alkaline earth metal disilicate or mixtures thereof.
  • the silicate salt of the alkaline earth metal and/or the disilicate salt of the alkaline earth metal is in amorphous form.
  • the alkaline earth metal compound present in the reaction is magnesium sulphate or magnesium chloride, more preferably magnesium sulphate.
  • the in-situ intermediate mixture includes one or more compound selected from the group consisting of magnesium hydroxide, magnesium silicate, magnesium disilicate or mixtures thereof. More preferably the intermediate mixture includes magnesium silicate, magnesium disilicate or mixtures thereof.
  • the alkali metal silicate is sodium silicate.
  • the intermediate mixture includes 0 wt.% zeolite.
  • the reaction of the alkali metal silicate salt with the alkaline earth metal salt is carried out by heating the aqueous mixture with or without agitation, preferably with agitation in a mixer at a temperature of 20°C to 80°C, more preferably from 70°C to 80°C.
  • the reaction is carried out for a duration of 0.5 minutes to 30 minutes by continuously stirring the aqueous mixture in the slurry handling system.
  • the alkaline earth metal salt may be pre-dissolved in water and before reacting with the alkali metal silicate in the aqueous mixture.
  • the intermediate mixture may include some amount of the unreacted alkaline earth metal compound or salt.
  • the aqueous mixture preferably includes detersive surfactant, preferably any unreacted alkaline earth metal salt and water.
  • the organic carboxylic acid salt of alkaline earth metal includes one or more of alkaline earth metal salt organic carboxylic acid, di-alkaline earth metal salt organic carboxylic acid, tri alkaline earth metal salt organic carboxylic acid or mixtures thereof.
  • the organic carboxylic acid salt of alkaline earth metal is a citric acid salt of magnesium, preferably comprising one or more of magnesium citrate, magnesium dicitrate, magnesium tricitrate or mixtures thereof.
  • the amount of water is not less than 22 wt.%, still preferably not less than 23 wt.%, more preferably not less than 24 wt.%, still more preferably not less than 25 wt.%, but typically not more than 40 wt.%, preferably not more than 38 wt.% or still preferably not more than 37 wt.% and most preferably not more than 35 wt.%.
  • the spray dried detergent particle may be used for preparing an unit dose product wherein the spray-dried detergent particle is enclosed in a pouch, preferably a water-soluble pouch, more preferably a water-soluble pouch comprising a film forming polymer selected from polyvinyl alcohol, polyvinylpyrrolidone and other known film forming polymer.
  • the laundry detergent composition includes from 5 wt.% to 100 wt.% spray-dried detergent particle according to the second aspect of the present invention. More preferably from 20 wt.% to 95 wt.%, still preferably from 30 wt.% to 95 wt.% of the spray-dried detergent particle obtainable according to the first aspect of the present invention.
  • Suitable fluorescent brighteners include dis-styryl biphenyl compounds example Tinopal ® CBS-X, di-amino stilbene di-sulfonic acid compounds, e.g. Tinopal ® DMS pure Xtra and Blankophor ® HRH, and Pyrazoline compounds, e.g. Blankophor ® SN, and coumarin compounds, e.g. Tinopal ® SWN.
  • Preferred brighteners are: sodium 2 (4-styry)-3-sulfophenyl)-2H-napthol(1,2-d]triazole, disodium 4,4'bis ⁇ [4-anilino-6-(N methyl-N-2 hydroxyethyl)amino 1,3,5-triazin-2-yl)]amino]stilbene-2-2' disulfonate, disodium 4,4'bis([(4-anilino-6-morpholino-l,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2'disulfonate, and disodium 4,4'- bis(2-sulfostyryl)biphenyl.
  • a suitable fluorescent brightener is S C.I. Fluorescent Brightener 260, which may be used in its beta or alpha crystalline forms, or a mixture of these forms.
  • the composition of the present invention preferably includes an enzyme. It may preferably include one or more enzymes. Preferred examples of the enzymes include those which provide cleaning performance and/or fabric care benefits.
  • suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, xyloglucanase, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, G-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof.
  • a packaged article comprising a flexible container enclosing a laundry detergent composition having a spray dried detergent particle prepared according to the first aspect of the present invention.
  • the flexible container is preferably made from a packaging material suitable for packaging laundry detergent composition the packaging material includes but is not limited to polyolefin film, laminates, paper based films or laminates, multilayered structures including two or more flexible structures and other materials known to a person skilled in the art.
  • the flexible container includes polyethylene films having polymer selected from HDPE, LLDPE, mLLDPE, LDPE or combination thereof.
  • the flexible films may be made of monomaterial or combination of different materials.
  • the flexible packaging container is a flexible pouch or a bag.
  • the laundry detergent composition comprising the spray dried detergent particle of the present invention may be packaged as unit dose product enclosed within a polymeric film, wherein the polymeric film is water soluble or disintegrates upon addition to the wash water.
  • the spray-dried detergent particle or a laundry detergent composition including the spray-dried detergent particle of the invention may be supplied in multidose plastics packs with a top or bottom closure.
  • a method of laundering fabric using a spray dried detergent particle or a laundry composition comprising a spray dried detergent particle according to the present invention which method involves the step of diluting an amount of the laundry detergent composition with water to obtain a wash liquor followed by the step of washing fabrics with the wash liquor so formed.
  • a measured amount of detergent composition dose
  • the dilution step preferably provides a wash liquor having from 3 to 20 g/wash of detersive surfactants (as are further defined above).
  • the product obtainable by a process according to the present invention has different product characteristics due to its process of manufacture.
  • the product has good physical properties, such as good cake strength and good flowability.
  • the product also has good dispensing properties, dissolution, and minimal fabric residue deposition. This is due to the in-situ formation of organic carboxylic acid of alkaline earth metal.
  • Example 1 Process for preparing the spray-dried detergent particle according to the present invention
  • a spray-dried detergent particle according to the present invention was prepared by adding water, alkaline source (sodium hydroxide, 50% active content) and acid form of the anionic surfactant (LAS acid, 97% active content) to a mixing unit to form sodium LAS in-situ.
  • alkaline source sodium hydroxide, 50% active content
  • acid form of the anionic surfactant LAS acid, 97% active content
  • the intermediate mixture was prepared by reacting the magnesium sulphate (alkaline earth metal salt) and sodium silicate with a SiO 2 :Na 2 O ratio of 2.4 (alkali metal silicate salt 47% active content) followed by the addition of citric acid (organic carboxylic acid).
  • citric acid organic carboxylic acid
  • the aqueous mixture pH is brought down to 3.
  • the citric acid reacts with the intermediate mixture to form magnesium citrate in the base mixture.
  • the pH of the base mixture was raised in two steps by first adding an aqueous solution having 50% concentration sodium hydroxide and then sodium silicate was added to form an aqueous slurry.
  • the final pH of the aqueous slurry was maintained at 8.5.
  • Table 1 Preparing an aqueous slurry according to the invention Ingredients Order of addition Quantity (Kg) Temperature (°C) pH Water 1 273.52 40 Sodium hydroxide 1 59.52 47 LAS Acid (97%) 2 229.96 80 2.4 R Sodium Silicate (47%) Heating On 3 33.82 79 Magnesium Sulphate (100%) Heating On 4 79.47 78 Citric Acid Heating On 5 53.24 78 3 Sodium sulphate (filler) Heating On 6 453.23 77 Sodium hydroxide (50%) Heating On 7 55.40 80 6 2.4 R Sodium silicate (47%) Heating On 8 19.00 80 8.5 Total slurry batch size (kg) 1266
  • composition of the prepared aqueous slurry was as given below in Table 1A
  • Table 1A Ingredients Ex 1 (wt.%) Na LAS 18.71 Magnesium Citrate 0.36 Magnesium disilicate 0.67 Sodium Citrates (monosodium, disodium, trisodium or mixtures thereof) 5.10 Magnesium Sulphate 0.52 Sodium Silicate 0.70 Sodium Sulphate 36.34 Sodium carbonate 0 NDOM 0.82 Water 36.76 TOTAL 100
  • aqueous detergent slurry was spray dried in a counter-current spray drying tower.
  • the aqueous detergent slurry was heated to 80°C and pumped under pressure (7.5 ⁇ 106 Nm- 2 ), into a counter current spray-drying tower with an air inlet temperature ranging from between 250°C to 330°C.
  • the inlet fan was set to provide a tower inlet airflow of 187,500 kgh -1 .
  • the exhaust fan was controlled to create a negative pressure in the tower of -200 Nm -2 (typically the outlet air flow rate through the exhaust fan is between 220,000 kgh -1 to 240,000 kgh -1 , this includes the evaporated water from the slurry).
  • the aqueous slurry was atomised into the tower where the atomised slurry was dried to produce a spray-dried detergent particle, which was then cooled and sieved to remove oversize material (> 1.8mm).
  • the spray dried detergent particle obtained was found to be free-flowing. Fine material ( ⁇ 0.175mm) was elutriated along with the exhaust air coming out of the spray-drying tower and was later collected in a post tower containment system.
  • the spray-dried detergent particle had a moisture content of 2.0 wt.%, a bulk density of 350g/L and a particle size distribution such that greater than 90 wt.% of the spray-dried detergent particle has a particle size ranging from 175 to 710 micrometres.
  • the temperature of the spray-dried detergent particle exiting the tower has a temperature of below 150°C.
  • the composition of the spray-dried detergent particle obtained by spray-drying the aqueous detergent slurry is given below.
  • Table 2 Spray dried particle according to the present invention Ingredients Ex 1 (wt.%) Na LAS 30 Magnesium Citrate 0.56 Magnesium disilicate 1.04 Sodium Citrates (monosodium, disodium, trisodium) 7.91 Magnesium Sulphate 0.81 Sodium Silicate 1.09 Sodium Sulphate 55.32 Sodium carbonate 0 NDOM 1.28 Water 2.0 TOTAL 100
  • the spray-dried particle was collected and characterized for the storage behaviour.
  • Spray-dried detergent particle according to the present invention (Ex 1) was evaluated for the powder properties using the compression test method. The caking tendency of the spray dried particle was measured and compared with the comparative examples.
  • Example 2A Evaluation of the storage behaviour of a spray dried detergent particle according to the present invention and comparative examples with higher pH
  • the storage behaviour of the spray dried detergent particle according to the present invention was evaluated along with comparative spray dried detergent particle having higher pH.
  • a control spray dried detergent particle Control
  • both silicate and carbonate were added at conventional levels for providing good powder structuring properties.
  • a first comparative example (Ex A) high levels of carbonate were used for structuring, but the spray dried particle had no silicate.
  • a second comparative example (Ex B) carbonate levels of Ex A were maintained, and a low amount of silicate was also added.
  • silicate was used for providing the structuring and no carbonate was used.
  • the collected spray-dried particle was packed and sealed in packs with a water vapour transmission ⁇ 5 gram/m 2 /day.
  • the packs were then stored for 8 weeks and 12 weeks at a temperature of 45°C and relative humidity of 80RH.
  • the data in table 3 shows that the spray-dried detergent particle according to the present invention having no carbonate and no silicate and having an in-situ formed magnesium citrate provided good storage properties and the spray-dried particle was free flowing even after 12 weeks and had slightly better powder properties than the control wherein the control powder has higher pH and high levels of carbonate and silicate.
  • the comparative Ex A with high levels of carbonate but no silicate was not processable due to slurry thickening, while Ex B and Ex C did not show good storage properties.
  • Example 2B Evaluation of the storage behaviour of a spray dried detergent particle according to the present invention and comparative examples with alternate ingredients for providing good powder properties
  • the storage behaviour of the spray dried detergent particle according to the present invention was evaluated along with comparative spray dried detergent particle having alternate ingredients for providing good powder properties.
  • a first comparative example (Ex D) pre-formed silica was added for structuring.
  • a second comparative example (Ex E) in-situ formed sodium citrate was used for structuring along with pre-formed added silica.
  • In-situ sodium citrate was formed by reacting citric acid with sodium hydroxide in the slurry which was thereafter spray-dried.
  • silica and sodium citrate which were formed in-situ was used for improving the powder properties.
  • the silica was formed by reacting citric acid with sodium silicate during slurry making.
  • the active was Na LAS made in-situ during the slurry making by reacting Las acid with sodium hydroxide as per stoichiometry.
  • the collected spray-dried particles were packed and sealed in packs having a water vapour transmission ⁇ 5 gram/m 2 /day.
  • the packs were then stored for 8 weeks and 12 weeks at a temperature of 45°C and relative humidity of 80RH.
  • Example 4 The data in table 4 demonstrates that the spray-dried detergent particle according to the present invention (Ex 1) having no carbonate and no silicate and structured using magnesium citrate provided good storage properties and the powder was free flowing even after 12 weeks.
  • Example E and Ex F other comparative powders having in-situ formed ingredients for providing good powder properties (silica and/or sodium citrate) showed higher propensity to cake over extended storage time (12 weeks for Ex E and 8 weeks for Ex F). It was also found that Ex D having added silica had a higher propensity to cake even immediately after spray-drying.
  • Example 1 the powder properties of the spray dried particle made according to the present invention (Ex 1) is better in terms of storage behaviour and the spray-dried particle has good powder properties and is free flowing both measured after freshly prepared as well as post prolonged storage where the spray-dried particle had a detersive active content of 30 wt.% and sulphate as a preferred filler.

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Claims (15)

  1. Verfahren zur Herstellung eines sprühgetrockneten Waschmittelpartikels, das die Schritte umfasst:
    (i) Umsetzen eines Alkalimetallsilikatsalzes und einer Erdalkalimetallverbindung in einer wässrigen Mischung, um in situ eine Zwischenmischung zu bilden, die eine oder mehrere Verbindungen enthält, ausgewählt aus der Gruppe, bestehend aus einem Erdalkalimetallhydroxid, Erdalkalimetallsilikatsalz, Erdalkalimetalldisilikatsalz oder Mischungen davon;
    (ii) Inkontaktbringen der Zwischenmischung, die eine oder mehrere Verbindungen enthält, ausgewählt aus der Gruppe, bestehend aus Erdalkalimetallhydroxid, Erdalkalimetallsilikat, Erdalkalimetalldisilikat oder Mischungen davon, mit einer organischen Carbonsäure in der wässrigen Mischung, um eine Basismischung zu bilden, die ein organisches Carbonsäuresalz eines Erdalkalimetalls umfasst;
    (iii) Hinzufügen einer Menge einer alkalischen Quelle zu der Basismischung, um eine wässrige Aufschlämmung mit einem pH-Wert in dem Bereich von 4 bis 8,5 bereitzustellen, wobei die wässrige Aufschlämmung ein organisches Carbonsäuresalz eines Erdalkalimetalls und ein Reinigungstensid umfasst;
    (iv) Sprühtrocknen der wässrigen Aufschlämmung zur Bildung eines sprühgetrockneten Waschmittelpartikels.
  2. Verfahren nach Anspruch 1, wobei die wässrige Aufschlämmung ein Disilikat- oder Silikatsalz eines Erdalkalimetalls umfasst.
  3. Verfahren nach Anspruch 1 oder 2, wobei die Erdalkalimetallverbindung aus der Gruppe, bestehend aus Magnesiumsulfat, Magnesiumchlorid oder Mischungen davon, ausgewählt ist.
  4. Verfahren nach Anspruch 1 oder 3, wobei das Alkalimetallsilikatsalz Natriumsilikat ist.
  5. Verfahren nach irgendeinem der vorhergehenden Ansprüche, wobei die wässrige Aufschlämmung außerdem ein in situ gebildetes organisches Carbonsäuresalz eines Alkalimetalls umfasst, das durch die Reaktion der organischen Carbonsäure mit der alkalischen Quelle gebildet wird.
  6. Verfahren nach irgendeinem der vorhergehenden Ansprüche, wobei die alkalische Quelle aus der Gruppe, bestehend aus Natriumhydroxid, Kaliumhydroxid, Natriumsilikat oder Mischungen davon, ausgewählt ist.
  7. Verfahren nach irgendeinem der vorhergehenden Ansprüche, wobei die organische Carbonsäure eine monomere organische Polycarbonsäure, vorzugsweise Citronensäure ist.
  8. Verfahren nach irgendeinem der vorhergehenden Ansprüche, wobei die wässrige Aufschlämmung nicht mehr als 2 Gew.-% Alkalimetallsilikat umfasst.
  9. Verfahren nach irgendeinem der vorhergehenden Ansprüche, wobei das Reinigungstensid ein anorganisches Tensid ist, das vorzugsweise aus der Gruppe, bestehend aus Alkylbenzolsulfonat, Alkylethersulfat, Alkylsulfat oder Mischungen davon, ausgewählt ist.
  10. Verfahren nach Anspruch 9, wobei das Alkylbenzolsulfonat ein lineares Alkylbenzolsulfonat-Tensid mit einer C10- bis C18-Alkylgruppe ist.
  11. Verfahren nach irgendeinem der vorhergehenden Ansprüche, wobei das organische Carbonsäuresalz eines Erdalkalimetalls ein Citronensäuresalz von Magnesium ist, bevorzugt umfassend eines oder mehrere der folgenden Salze: Magnesiumcitrat, Magnesiumdicitrat, Magnesiumtricitrat oder Mischungen davon.
  12. Verfahren nach irgendeinem der vorhergehenden Ansprüche, wobei die wässrige Aufschlämmung ein Carboxylatpolymer umfasst.
  13. Verfahren nach irgendeinem der vorhergehenden Ansprüche, wobei die wässrige Aufschlämmung umfasst:
    (i) 2 bis 35 Gew.-% Reinigungstensid;
    (ii) 0,1 bis 4 Gew.-% organisches Carbonsäuresalz eines Erdalkalimetalls;
    (iii) bevorzugt 1 bis 12 Gew.-% organisches Carbonsäuresalz eines Alkalimetalls;
    (iv) bevorzugt 0 bis 2,5 Gew.-% Silikat- und/oder Disilikatsalz eines Erdalkalimetalls;
    (v) bevorzugt 0 bis 1,5 Gew.-% nicht umgesetztes Erdalkalimetallsalz;
    (vi) bevorzugt 15 bis 70 Gew.-% Füllstoff; und
    (vii) 20 bis 40 Gew.-% Wasser.
  14. Sprühgetrocknetes Waschmittelpartikel, erhältlich nach irgendeinem der vorhergehenden Ansprüche, umfassend:
    (i) 3 bis 50 Gew.-% Reinigungstensid;
    (ii) 0,2 bis 6 Gew.-% organisches Carbonsäuresalz eines Erdalkalimetalls;
    (iii) bevorzugt 2 bis 20 Gew.-% organisches Carbonsäuresalz eines Alkalimetalls;
    (iv) bevorzugt 0 bis 4 Gew.-% Silikat- und/oder Disilikatsalz eines Erdalkalimetalls;
    (v) bevorzugt 0 bis 2 Gew.-% nicht umgesetztes Erdalkalimetallsalz;
    (vi) bevorzugt 25 bis 88 Gew.-% Füllstoff; und
    (vii) bevorzugt 1 bis 3,5 Gew.-% Feuchtigkeitsgehalt.
  15. Waschmittelzusammensetzung, umfassend 5 bis 100 Gew.-% sprühgetrocknete Partikel nach Anspruch 14.
EP22785949.3A 2021-09-15 2022-09-12 Verfahren zur herstellung eines sprühgetrockneten waschmittelpartikels Active EP4402232B1 (de)

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PCT/EP2022/075217 WO2023041461A1 (en) 2021-09-15 2022-09-12 Process for preparing a spray dried detergent particle

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025045969A1 (en) * 2023-08-30 2025-03-06 Unilever Ip Holdings B.V. Solid laundry composition
WO2025045982A1 (en) * 2023-08-30 2025-03-06 Unilever Ip Holdings B.V. Solid laundry composition

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4239486A (en) 1979-04-27 1980-12-16 Gomez Manuel D Thawing assembly for clogged asphalt pipes
EP0221777A2 (de) 1985-11-01 1987-05-13 Unilever Plc Reinigungsmittel
US20110147962A1 (en) * 2009-12-18 2011-06-23 Larry Savio Cardozo Spray-Drying Process
EP3546556A1 (de) 2018-03-28 2019-10-02 The Procter & Gamble Company Verfahren zur herstellung von sprühgetrocknetem waschmittelpartikel

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4139486A (en) * 1977-03-22 1979-02-13 The Procter & Gamble Company Built detergent composition
US4294718A (en) 1980-03-10 1981-10-13 Colgate-Palmolive Company Non-gelling inorganic salt crutcher slurries
CA2001927C (en) 1988-11-03 1999-12-21 Graham Thomas Brown Aluminosilicates and detergent compositions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4239486A (en) 1979-04-27 1980-12-16 Gomez Manuel D Thawing assembly for clogged asphalt pipes
EP0221777A2 (de) 1985-11-01 1987-05-13 Unilever Plc Reinigungsmittel
US20110147962A1 (en) * 2009-12-18 2011-06-23 Larry Savio Cardozo Spray-Drying Process
EP3546556A1 (de) 2018-03-28 2019-10-02 The Procter & Gamble Company Verfahren zur herstellung von sprühgetrocknetem waschmittelpartikel

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