WO2011061045A1 - Granulé de détergent et son procédé de fabrication - Google Patents

Granulé de détergent et son procédé de fabrication Download PDF

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Publication number
WO2011061045A1
WO2011061045A1 PCT/EP2010/066159 EP2010066159W WO2011061045A1 WO 2011061045 A1 WO2011061045 A1 WO 2011061045A1 EP 2010066159 W EP2010066159 W EP 2010066159W WO 2011061045 A1 WO2011061045 A1 WO 2011061045A1
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WIPO (PCT)
Prior art keywords
surfactant
sodium carbonate
acid
detergent
granule
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PCT/EP2010/066159
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English (en)
Inventor
Andrew Paul Chapple
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Unilever Nv
Unilever Plc
Hindustan Unilever Limited
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Application filed by Unilever Nv, Unilever Plc, Hindustan Unilever Limited filed Critical Unilever Nv
Publication of WO2011061045A1 publication Critical patent/WO2011061045A1/fr

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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
    • C11D11/04—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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/37—Polymers
    • 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

Definitions

  • Pending PCT application PCT/EP2009/054757 discloses a process for dry neutralisation using habit modified carbonate. It says that other anionic surfactants can be co formulated with the surfactant acid being dry neutralised but the disclosure of this is limited to adding the neutralised surfactant, such as a SLES paste, together with the unneutralised surfactant acid before the dry neutralisation takes place.
  • EP1165735B Unilever: Detergent Powder Composition. This document discloses a process for the preparation of a granular detergent product comprising contacting a liquid binder
  • the component comprising an acid precursor of an anionic surfactant and a hydrotrope with a solid particulate starting material comprising a neutralising agent in a low shear mixer and granulating the mixture, wherein the acid precursor of the anionic surfactant is at least 75 wt% of the liquid binder and wherein the total amount of water in the liquid binder is not more than 15 wt%, and in which the acid precursor of the anionic surfactant and the hydrotrope are added substantially simultaneously to the mixer.
  • surfactants i.e. neutralised salts
  • the liquid binder should be pumpable and capable of being delivered to the low shear mixer in a fluid, including paste-like, form.
  • Suitable anionic surfactants are well-known to those skilled in the art.
  • liquid binder examples include alkylbenzene sulphonates, particularly linear
  • alkylbenzene sulphonates having an alkyl chain length of C8- C15; primary and secondary alkyl sulphates, particularly C12- C15 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; dialkyl sulphosuccinates ; and fatty acid ester sulphonates.
  • Sodium salts are generally preferred.
  • dodecylsulphonic acid and mixed to form a doughy mass.
  • the sodium alkyl sulphate is added as low moisture paste (75wt %) alkyl sulphate, at 60°C.
  • the mixing time for this step of the process is 75 seconds.
  • step E The doughy mass formed in steps A-D (which has about 12 % water) is then granulated using sodium aluminosilicate (SAS) powder.
  • Hydrated zeolite A is the SAS used. It has an average particle diameter of from 32 to 5 microns.
  • the SAS is added to the doughy mass over a period of 45 seconds.
  • the tip speed for the rotor of the Eirich mixer is 33 m/sec during the addition of the deagglomerating agent (SAS) .
  • the mass is then post-mixed for approximately 3 minutes to allow the dough granulation to complete .
  • This document uses PAS in step B and it suggests that the delayed addition of a surfactant paste in a conventional dry neutralisation process results in a doughy mass that must be further granulated with zeolite in order to form detergent granules .
  • US5482646A discloses a composition for cold water laundering of fabrics with minimal detergent residue in the wash water.
  • a particulate ingredient sodium stearate is exemplified
  • detergent granules to form an adherent coating of fine particles on the detergent granules, in a quantity that is effective for reducing the residue of undissolved detergent under cold water laundering conditions.
  • sodium salts of particulate anionic surfactants could also be coated onto the surface in place of the sodium stearate.
  • SLES is one such surfactant. SLES paste could not be used in this process .
  • WO9407990A Henkel, describes how detergent anionic surfactant granules of high anionic surfactant content can be produced by neutralization of anionic surfactants in their acid form using a powdered neutralizer, with simultaneous granulation and, as needed, simultaneous drying.
  • this involves the neutralization of fatty alcohol sulphonic acids, alkyl benzene- sulphonic acids and/or alpha-alkylsulphonic acid methyl ester acids with an excess of sodium carbonate, and the simultaneous granulation with other liquid components, in particular with anionic surfactant pastes, aqueous hydrogen peroxide solution and/or a zeolite suspension.
  • This production can be effected in any apparatus in which neutralization can be carried out simultaneously with granulation and drying.
  • this preparation takes place in a continuous fluidized bed system.
  • the paste exemplified is 54 wt% TAS . It is added simultaneously with the surfactant acid.
  • W098/14557, P&G contains a number of examples using dry neutralisation.
  • a granule is formed in a first mixer by dry neutralisation of LAS acid with sodium carbonate. Then in a different mixer a solution of 28% solids SLES is sprayed onto the agglomerates for further agglomeration. Such a dilute solution is not a paste. It is necessary to handle the output of such a mixer very carefully due to the large amount of water that has been added. The driving off of such a large amount of water from the detergent granule is energy
  • sequential two step process for the manufacture of detergent granules comprising a mixed anionic non-soap surfactant system comprising a first step of dry neutralisation and granulation of surfactant acid with a stoichiometric excess of habit modified Sodium Carbonate, which is a crystal growth modified Sodium Carbonate that comprises a mixture of Sodium Carbonate and polymer, to give a first granule comprising neutralised surfactant acid, polymer and the excess habit modified sodium carbonate, followed by a second step of
  • surfactants like SLES and PAS, are better added as a paste after the granule is formed by dry neutralisation of surfactant acid, especially LAS acid, with habit modified carbonate.
  • the paste surfactant used in the second step is selected from ethoxylated and unethoxylated Sodium alkyl sulphate and mixtures thereof.
  • the most preferred paste is SAES.
  • SAES is sodium alkyl ether sulphate.
  • the alkyl group is lauryl and the material is then SLES. SLES is good at boosting detergent performance on some stains and may be used with LAS in calcium tolerant surfactant blends.
  • the degree of ethoxylation is from 1 to 3.
  • 1EO material is, in fact, a blend of SLES with PAS.
  • paste we mean that the active content of the material added to the agglomeration step is at least 50wt% solids, preferably it is greater than 65wt% solids, the balance being essentially water. A paste with a water content of less than 45wt% is desirable.
  • the surfactant acid used in the first step may comprise a major part of LAS acid, preferably used in liquid form.
  • the surfactant acid is advantageously reacted while mixing with a molar excess of habit modified Sodium Carbonate to form sodium salt of the anionic surfactant, while mixing so that agglomeration occurs simultaneously.
  • the mixing is
  • the mixing is carried out in a mixer, which has both a stirring action and a chopping or cutting action, and both actions are used during the dry neutralisation reaction.
  • the invention also provides a high active detergent granule comprising :
  • surfactant comprising:
  • SLES Sodium alkyl sulphate
  • PAS unethoxylated Sodium alkyl sulphate
  • habit modified Sodium Carbonate which is a crystal growth modified Sodium Carbonate that comprises a mixture of Sodium Carbonate and polymer, and c) less than 10 wt%, preferably zero, zeolite,
  • the detergent granule may further comprise perfume.
  • the detergent granule may further comprise nonionic surfactant.
  • the detergent granule may further comprise soap.
  • Habit modified Sodium Carbonate does not include habit modified Burkeite, although low concentrations of Burkeite could conceivably be included in admixture with the desired habit modified Sodium Carbonate provided that the resulting admixture remains characterised as described below. It is essential that the polymer used, as crystal growth modifier, is present when crystallisation of the habit modified Sodium Carbonate occurs, that is to say, it must be
  • Sodium Carbonate is incorporated not later than the Sodium Carbonate.
  • Habit modified Sodium Carbonate is further characterised by its specific surface area, measured by nitrogen adsorption.
  • the specific surface area ("SSA") of the Sodium Carbonate is measured by nitrogen absorption according to ASTM D 3663-78 standard based upon the Brunauer, Emmett, and Teller (BET) method described in J. Am. Chem. Soc. 60, 309 (1938) .
  • BET Brunauer, Emmett, and Teller
  • the Habit modified Sodium Carbonate is characterised by having a specific surface area (SSA) of 5 m 2 /g or greater, preferably 8 m 2 /g or greater, even more preferably 10 m 2 /g or greater.
  • SSA specific surface area
  • the pore volume in pores less than 2 micron may further be provided.
  • An alternative characterisation of the habit modified Sodium Carbonate, comprising polymer and Sodium Carbonate, is to use it in the process of claim 1 with sulphonic acid and to determine the maximum Sodium Sulphonate anionic non-soap surfactant levels achievable before over-granulation occurs.
  • Over-granulation means that the discrete detergent granules begin to coalesce into a sticky mass and it is no longer possible to discharge them as a free flowing product without adding flow aid or other solid materials such as Zeolite or Sodium Tripolyphosphate .
  • the anionic Sodium Sulphonate surfactant level achieved is greater than 30 wt%, preferably greater than 35 wt%, more preferably greater than 45 wt%, then the Sodium Carbonate is habit modified for the purposes of this invention .
  • HMC Habit modified Sodium Carbonate
  • spray drying as described in EP 0 221 776 and WO 2006/081930.
  • Alternative drying methods as described in those patent applications, may also be employed: for example, air drying, oven drying, drum drying, ring drying, freeze drying, solvent drying, or microwave drying.
  • HMC can also be made by precipitation of a saturated Sodium
  • Carbonate solution which further comprises a growth modifying polymer, in an evaporator, separating the precipitate; e.g. by filtration and drying the precipitate to habit modified Sodium Carbonate.
  • the remaining solution is augmented with fresh
  • Suitable crystal growth modifying polymers may be selected from polycarboxylates .
  • Polyaspartates and polyaspartic acid are advantageously used due to their biodegradability .
  • Preferred polymeric polycarboxylate crystal growth modifiers used in the invention are used in amounts of from 0.1 to 20 wt%, preferably from 0.2 to 5 wt%, most preferably 1 to 5 wt%, based on the total amount of Sodium Carbonate.
  • higher levels of polymer for example, up to 60% by weight based on Sodium Carbonate, may be present in detergent granules of the invention, or full compositions comprising the detergent granules of the invention, for reasons other than crystal growth modification, for example, building, structuring or antiredeposition .
  • the polycarboxylate crystal growth modifier preferably has a molecular weight of at least 1000, advantageously from 1000 to 300 000, especially from 1000 to 250 000.
  • copolymers of acrylic acid or maleic acid are of especial interest.
  • polyacrylates and acrylic acid/maleic acid copolymers are of especial interest.
  • Suitable polymers which may be used alone or in combination, include the following:
  • Salts of polyacrylic acid such as sodium polyacrylate, for example Versicol (Trade Mark) E5 E7 and E9 ex Allied Colloids, average molecular weights 3500, 27 000 and 70 000; Narlex
  • a second group of polymeric crystal growth modifiers comprises polyaspartic acids and polyaspartates .
  • modifiers having molecular weights in the 3500 to 100000 range, especially 4000 to 70000 and more especially 5000 to 70000. All molecular weights quoted herein are those provided by the manufacturers .
  • Polyaspartate is a biopolymer synthesised from L-aspartic acid, a natural amino acid. Due in part to the carboxylate groups, polyaspartate has similar properties to polyacrylate .
  • One preferred type of polyaspartate is thermal polyaspartate or TPA. This has the benefit of being biodegradable to
  • TPA may be made by first heating aspartic acid to temperatures above 180 °C to produce polysuccinimide . Then the polysuccinimide is ring opened to form polyaspartate . Because the ring can open in two possible ways, two polymer linkages are observed, an [alpha] -linkage and a [beta] -linkage . Amounts of from 0.1 to 20 wt% of the crystal growth modifier, preferably from 0.2 to 5 wt%, most preferably 1 to 5 wt%, based on the total amount of Sodium Carbonate are generally
  • Carbonate may be of any type. Synthetic light soda ash has been found to be especially preferred; natural heavy soda ash is intermediate, while synthetic granular soda ash is the least preferred raw material.
  • the surfactant acid is an acid precursor of an anionic non-soap surfactant which, when reacted with habit modified Sodium
  • Carbonate will be neutralised to form the sodium salt of the anionic surfactant.
  • Surfactant acids in liquid, pumpable, form are preferred.
  • a preferred class of anionic surfactants is alkyl aryl
  • the preferred surfactant acid is linear alkyl benzene sulphonic acid, also referred to as LAS acid and HLAS .
  • This surfactant acid gives a corresponding linear alkyl benzene sulphonate (LAS) upon neutralisation.
  • the LAS non- soap anionic surfactant has an alkyl chain length of C8-18, more preferably ClO-16 and most preferably C12-14.
  • a second preferred class of anionic surfactant is the alkyl and/or alkenyl sulphuric acid half-esters (i.e. the sulphation products of primary alcohols) which give alkyl and/or alkenyl sulphates upon neutralisation.
  • anionic surfactants is primary alcohol sulphate (PAS) , especially PAS having a chain length of ClO-22, preferably C12-14; Coco PAS is particularly desirable.
  • the surfactant acid (or mixture of surfactant acids) may be used in a partially pre-neutralised form without loss of the advantageous effects of the invention. In effect, the
  • surfactant acid is then a mixture of the surfactant acid with neutralised anionic non-soap surfactant.
  • optionalal further ingredients present during the process are then a mixture of the surfactant acid with neutralised anionic non-soap surfactant.
  • the HMC dry neutralisation process has all of the advantages and flexibility of prior art dry neutralisation processes.
  • the surfactant acid may be added in admixture with other liquid components.
  • other liquid components in addition to the fatty acids and neutralised anionic surfactant already discussed, the most important additional component that may be added as liquids with the surfactant acid is nonionic surfactant. This is typically added to the surfactant acid to reduce viscosity to enable it to be added at a lower temperature.
  • Suitable nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C8- C20 aliphatic alcohols ethoxylated with an average of from 1 to 50, preferably 1 to 20, moles ethylene oxide per mole of alcohol, and more especially the do-cis primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
  • Non-ethoxylated nonionic surfactants include alkyl-polyglycosides , glycerol monoethers, and polyhydroxyamides (glucamide) .
  • neutralised anionic surfactant may be mixed with the surfactant acid. This can have the advantage of increasing throughput of the reaction vessel/mixer.
  • liquid additives that may be added with the anionic surfactant acid, or added as separate liquid stream (s) , include inorganic acids, such as sulphuric acid, and hydrotropes, such as para toluene sulphonic acid.
  • Additional solid may be admixed with the habit modified Sodium Carbonate. This can be done either before or during
  • Carbonate i.e. soda ash
  • Zeolite and/or other builder materials could be added, although they are not needed to gain the good granule properties ascribed to the use of HMC . Indeed, it is preferred to avoid use of zeolite completely, except perhaps as a final whitening coating.
  • a complete detergent system can nevertheless be formulated into a single simple dry neutralised granule especially when Calcium tolerant surfactant blends are used.
  • Calcium tolerant surfactant blends are those single or mixed surfactants, which do not require builders to be present for effective detergency across a normal range of water hardness. We use the following method to test a
  • surfactant blend for Calcium-tolerance First 0.7 g/L of the surfactant blend are dissolved in water containing sufficient Calcium ions to give a French hardness of 40 (4 x 10 ⁇ 3 Molar Ca 2+ ) . Other electrolytes such as Sodium Chloride, Sodium Sulphate, and Sodium hydroxide are then added as necessary to adjust the ionic strength to 0.05M and the pH to 10. The adsorption of light of wavelength 540 nm through 4 mm of sample is measured 15 minutes after sample preparation. Ten
  • alkalinity in the product an excess of about 10 to 15 wt% is then suitable. This represents a molar excess of 3:1 or more.
  • the solids present in the mixer may also include other solid ingredients desired for inclusion in the detergent granule, for example, fluorescers ; polycarboxylate polymers;
  • antiredeposition agents for example, sodium carboxymethyl cellulose; or fillers such as sodium sulphate, diatomaceous earth, calcite, kaolin or bentonite.
  • solid particulate surfactants for example, alkylbenzene sulphonate and/or alkyl sulphate in powder form, may form part of the solids charge to the mixer to further increase the activity level of surfactant in the granule, however it is preferred to produce all the anionic surfactant by dry neutralisation.
  • anionic surfactants that may be present in detergent granules prepared by the process of the invention include secondary alkyl sulphates, alkyl ether sulphates, and dialkyl sulphosuccinates .
  • Anionic surfactants are of course well known and the skilled reader will be able to add to this list.
  • ingredients may be used in the dry neutralisation reaction. Because the system is self structuring, no zeolite or similar structurant is needed and the process is easy to control. The main thing that we have found for this process is to minimise the amount of water added in the dry neutralisation step as discussed earlier. When habit modified Sodium Carbonate is used in the dry
  • the resulting granule will comprise neutralised anionic surfactant together with any excess habit modified Sodium Carbonate.
  • the habit modified Sodium Carbonate is an excellent substrate for additional liquid components and it also functions in the same way as Sodium Carbonate as a buffer in a detergent composition.
  • the invention may thus advantageously be used to prepare detergent powders in which Sodium Carbonate is used without any other builder present - especially if a Calcium tolerant surfactant blend or mixture is used. To ensure the presence of significant quantities of
  • a process feature known to the person skilled in the art of dry neutralisation is that the surfactant acid should be added to the mixer sufficiently gradually so that it will be consumed immediately and will not accumulate in the mixer in unreacted form. We have found that this applies equally to the process using habit modified Sodium Carbonate.
  • the time required and preferred for addition of the surfactant acid is of course dependent on the amount to be added, but in general addition preferably takes place over a period of at least 1 minute, more preferably over a period of from 2 to 12 minutes, most
  • the process is generally not sensitive to the type of mixer used, provided intensive mixing is applied. We have found that to obtain the full advantages of the invention the use of a mixer with a chopping action is advantageous.
  • the HMC starting material has relatively low crush strength and the mixer should be selected so that it breaks up and rapidly provides fine, material with a consequent large total surface area for
  • the cutting action is the preferred chopping action. This may be advantageously achieved by the choice of mixer to be a high-speed mixer/granulator having both a
  • the high- speed mixer/granulator has rotatable stirrer and cutter
  • Such a mixer is capable of combining a high-energy stirring input with a cutting action, but can also be used to provide other, gentler stirring regimes with or without the cutter in operation. The cutters would be off during the solids pre- mixing .
  • a Lodige mixer is preferred, vertical or horizontal axis cutters are desirable for high anionic loading. Also preferred are mixers of the Fukae FS-G type manufactured by Fukae Powtech Co Ltd., Japan; this apparatus is essentially in the form of a bowl-shaped vessel accessible via a top port, provided near its base with a stirrer having a substantially vertical axis, and a cutter positioned on a side wall. The stirrer and cutter may be operated independently of one another, and at separately variable speeds. The vessel can be cooled.
  • Yet another mixer found to be suitable for use in the process of the invention is the Lodige (Trade Mark) FM series batch mixer ex Morton Machine Co. Ltd., Scotland. This differs from the mixers mentioned above in that its stirrer has a horizontal axis.
  • Z blade and sigma mixers are suitable mixers having a chopping action.
  • the temperature of the powder mass in the mixer should be maintained throughout at 55°C or below, preferably below 50°C, more preferably below 47°C, and desirably below 40°C. If the temperature is allowed to rise too much, agglomeration and lump formation may occur.
  • SLES paste is preferred to PAS paste because it can give a calcium tolerant surfactant blend with LAS.
  • both LAS and PAS pastes can be used.
  • a problem with these paste surfactants is that they are is sensitive to acid hydrolysis and normally should be kept away from dry neutralisation reactions. Surprisingly this does not appear to be the case when habit modified carbonate is used. This is probably due to the rapid completion of the reaction.
  • the preferred SLES is C12-14 3EO material. However, granulation with different SLES is also encompassed within the invention. Mixed SLES may also be used. It should be noted that SLES 1EO is actually a mixture of SLES and PAS. Addition of the neutralised paste surfactant
  • regranulates i.e. reagglomerates by breaking up the original granule and forms new homogeneous granules comprising both the LAS (for example) and the paste surfactant (SLES for example) .
  • LAS for example
  • SLES paste surfactant
  • the carrying capacity of the habit modified carbonate is so good and the dry neutralisation reaction so fast that we have found that the granules are sufficiently free flowing to be used without a drying step. This is especially useful if they are to be mixed with other components as it avoids an unnecessary process step.
  • the level of water in the paste should be a low as possible. Typically, it will be around 30 wt% water. I.e. 70 wt% active paste.
  • a second mixer which may either be the same or different from the first mixer, is used.
  • An advantage of the process using habit modified carbonate is that the granules produced in both stages are free flowing and can easily be transferred to an immediately following process stage without any significant alteration of granule properties. It is usual for the second step to follow the first step without any intermediate processing except for the possible transfer from one mixer to the next.
  • Calcium tolerant surfactant blends that may be dry neutralised include mixtures of LAS, optionally with nonionic high EO. To complete the blend it may be necessary to add SLES paste and/or AOS paste. We have found that it is unnecessary and
  • the granular product of the process is a particulate solid with a bulk density in the range 450 to 720 g/litre.
  • the particle size distribution is generally such that at least 50 wt%, preferably at least 70 wt% and more preferably at least 85 wt%, of particles are smaller than 1700 microns, and the level of fines is low. No further treatment has generally been found to be necessary to remove either oversize particles or fines.
  • the product generally has excellent flow properties, low compressibility and little tendency towards caking.
  • particulate detergent granules that are the direct result of the dry neutralisation process may have an anionic surfactant content of 25 wt% to 45 wt%, or even higher.
  • anionic surfactant content 25 wt% to 45 wt%, or even higher.
  • the absence of the need for a granulation aid such as zeolite, together with the ease that the reaction can be driven results in the potential to achieve exceptionally high levels of anionic surfactant in the granule.
  • greater than about 30 wt%, preferably greater than 35 wt%, even greater than 40 wt%, or over 45 wt% anionic surfactant may be incorporated into the detergent granule. It is preferred for the anionic surfactant to comprise less than 10 wt% soap, based on the total anionic surfactant in the detergent granule.
  • the detergent granules may also comprise water in an amount of 0 to 8% and preferably 0 to 4% by weight of the granules.
  • the detergent granules obtained from the process are storage stable at high levels of humidity. Thus, they can be used in a wide range of detergent products. Desirably the detergent granules have an aspect ratio not in excess of two and more preferably are generally spherical in order to reduce segregation from other particles in a
  • detergent granules may be admixed with anything normally used in
  • detergent formulations may be dry blended with solid materials and they may advantageously have further liquids added into them, using their spare liquid carrying capacity. It is especially advantageous to add conventional, or even higher than conventional, levels of perfume this way.
  • non-soap surfactant for example, cationic, zwitterionic, amphoteric or semipolar surfactants, may also be used with the granules if desired.
  • cationic, zwitterionic, amphoteric or semipolar surfactants may also be used with the granules if desired.
  • suitable detergent- active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and
  • the fully formulated composition may comprise up to 8 wt% soap.
  • Detergent compositions including the detergent granules prepared by the process of the invention may contain
  • antiredeposition agents such as cellulosic polymers; anti incrustation agents, perfumes, dyes, shading dyes, fluorescers, sodium silicate; corrosion
  • inhibitors including silicates; inorganic salts such as sodium sulphate, enzymes; coloured speckles; foam controllers; and fabric softening compounds.
  • the detergent granule may if desired be mixed with other organic or inorganic builders, typically supplied in the form of granules of either pure builder or mixtures of builder and other ingredients.
  • Especially preferred organic builders are acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, preferably from 1 to 10wt%. Such polymers may also fulfil the function of the habit modifying polymer .
  • the skilled detergent formulator can decide which ingredients are suitable for admixture in the mixer, and which are not.
  • a base powder for convenience, such other powder is hereinafter called a base powder.
  • the detergent granules produced by the present invention may be admixed with such other powders, a significant degree of formulation flexibility is obtained and the level of active material in the fully formulated composition may be very high without an unnecessary increase in builder levels.
  • the total amount of surfactant present in the detergent is the total amount of surfactant present in the detergent
  • composition is suitably from to 5 to 40 wt%, although amounts outside this range may be employed as desired.
  • the detergent granules may typically constitute from 30 to 100 wt% of a final fully formulated detergent composition.
  • the fully formulated detergent composition incorporating the detergent granules produced by the process of the invention may comprise from 5 to 45 wt%, preferably 10 to 35 wt% of anionic surfactant, this anionic surfactant being derived wholly or in part from the granular product of the dry neutralisation reaction.
  • the process of the invention is of especial interest for the production of detergent powders or components containing relatively high levels of anionic
  • the fully formulated detergent composition may comprise from 0 to 10 wt% of nonionic surfactant, and from 0 to 5 wt% of fatty acid soap.
  • Fully formulated detergent compositions comprising other ingredients and the detergent granules produced by dry
  • Habit modified carbonate suitable for use in the process is prepared as described in PCT/EP2009/054757 (C4610), and
  • the mixer was operated with a rotor speed of 350 rpm and a chopper speed of 1300 rpm. To the mixing powder was then added 323g of LAS acid (addition time approx 2
  • Example 1 50g of spray dried Habit modified carbonate from Example 1 was placed in the bowl of a Braun (MR 500 CA) mixer/ granulator. To the mixing powder was then added 12.2g of LAS acid (addition time approx 2 minutes) . After addition of the LAS acid, 15.2g of SLES paste (70% active) was finally added over a period of approximately 2 minutes.
  • MR 500 CA MR 500 CA
  • the mixer was operated with a rotor speed of 350 rpm and a chopper speed of 1300 rpm. To the mixing powder was then added 201. lg of LAS acid (addition time approx 2 minutes) . After addition of the LAS acid, 323g of SLES paste (70% Active) was finally added over a period of approximately 2 minutes .
  • Example 1 50g of spray dried Habit modified carbonate from Example 1 was loaded into the bowl of a Braun (MR 500 CA) mixer and the mixer started. To the mixing powder was then added 8.05g of LAS acid (addition time approx 2 minutes) . After addition of the LAS acid, 19.7g of SLES paste (70% active) was finally added over a period of approximately 2 minutes.
  • MR 500 CA MR 500 CA
  • Example 1 50g of spray dried Habit modified carbonate from Example 1 was loaded into the bowl of a Braun (MR 500 CA) mixer and the mixer started. To the mixing powder was then added 12. Og of LAS acid (addition time approx 2 minutes) . After addition of the LAS acid, 15.5g of SLES paste (70% active) was finally added over a period of approximately 2 minutes.
  • MR 500 CA MR 500 CA
  • Example 1 50g of spray dried Habit modified carbonate from Example 1 was loaded into the bowl of a Braun (MR 500 CA) mixer and the mixer started. To the mixing powder was then added 8.2g of LAS acid (addition time approx 2 minutes) . After addition of the LAS acid, 24. Og of PAS paste (70% active), heated to 60°C, was finally added over a period of approximately 2 minutes.
  • MR 500 CA MR 500 CA
  • Example 1 50g of spray dried Habit modified carbonate from Example 1 was loaded into the bowl of a Braun (MR 500 CA) mixer and the mixer started. To the mixing powder was then added 12.5g of LAS acid (addition time approx 2 minutes) . After addition of the LAS acid, 26.4g of PAS paste (70% active), heated to 60°C, was finally added over a period of approximately 2 minutes.
  • Example 1 50g of spray dried Habit modified carbonate from Example 1 was loaded into the bowl of a Braun (MR 500 CA) mixer and the mixer started. To the mixing powder was then added 25.2g of LAS acid (addition time approx 2 minutes) . After addition of the LAS acid, 20. Og of PAS paste (70% active), heated to 60°C, was finally added over a period of approximately 2 minutes.
  • MR 500 CA MR 500 CA

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  • Inorganic Chemistry (AREA)
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Abstract

La présente invention porte sur un procédé séquentiel en deux étapes permettant de fabriquer des granulés de détergent comprenant un système de tensioactif non-savon anionique mélangé. Ledit procédé comprend une première étape de neutralisation à sec et de granulation d'un acide tensioactif avec un excès stœchiométrique de carbonate de sodium à faciès modifié, qui est un carbonate de sodium à croissance cristalline modifiée qui comprend un mélange de carbonate de sodium et de polymère, pour donner un premier granulé comprenant l'acide tensioactif neutralisé, le polymère et le carbonate de sodium à faciès modifié en excès, suivie par une seconde étape de réagglomération du premier granulé avec un tensioactif pâteux, comprenant au moins 50 % en poids d'un tensioactif anionique neutralisé, pour donner les granulés de détergent comprenant un système de tensioactif non-savon anionique mélangé. L'invention porte également sur un granulé de détergent hautement actif pouvant être obtenu par ce procédé.
PCT/EP2010/066159 2009-11-20 2010-10-26 Granulé de détergent et son procédé de fabrication WO2011061045A1 (fr)

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EP09176663.4 2009-11-20

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023025685A1 (fr) 2021-08-27 2023-03-02 Unilever Ip Holdings B.V. Composition détergente

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0221776A2 (fr) 1985-11-01 1987-05-13 Unilever Plc Compositions détergentes, parties constituantes et leurs procédés de préparation
EP0438320A2 (fr) * 1990-01-19 1991-07-24 Unilever Plc Compositions détergentes et leur procédÀ© de préparation
WO1992006170A1 (fr) * 1990-10-03 1992-04-16 The Procter & Gamble Company Procede de preparation de compositions detersives de haute densite contenant un agent tensio-actif particulaire sensible au ph
US5178798A (en) 1989-06-09 1993-01-12 The Procter & Gamble Company Formation of detergent granules by deagglomeration of detergent dough
WO1994007990A1 (fr) 1992-09-30 1994-04-14 Henkel Kommanditgesellschaft Auf Aktien Procede de fabrication de granules tensioactifs
US5482646A (en) 1993-03-05 1996-01-09 Church & Dwight Co., Inc. Powder detergent composition for cold water laundering of fabrics
WO1998014557A1 (fr) 1996-10-04 1998-04-09 The Procter & Gamble Company Procede de production d'une composition detergente sans l'utilisation d'une tour
WO1999003964A1 (fr) 1997-07-14 1999-01-28 The Procter & Gamble Company Procede de production d'une composition detergente de faible densite par agglomeration controlee dans un sechoir a lit fluide
EP0936269A1 (fr) * 1996-09-06 1999-08-18 Kao Corporation Particules detergentes, procede pour preparer ces particules et composition detergente presentant une masse volumique apparente importante
WO2000017304A1 (fr) * 1998-09-18 2000-03-30 The Procter & Gamble Company Procede en continu de fabrication d'une composition de detergent
WO2002024854A1 (fr) * 2000-09-25 2002-03-28 Unilever Plc Production de granules de tensioactif anionique par neutralisation in situ
EP1165735B1 (fr) 1999-03-30 2005-10-26 Unilever Plc Composition detergente en poudre
WO2006081930A1 (fr) 2005-02-01 2006-08-10 Unilever Plc Materiau support au carbonate de sodium modifie
EP1534812B1 (fr) * 2002-09-06 2007-08-15 Kao Corporation Particules de detergent
WO2009141203A1 (fr) * 2008-05-22 2009-11-26 Unilever Plc Fabrication de granulés de détergent par neutralisation à sec

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0221776A2 (fr) 1985-11-01 1987-05-13 Unilever Plc Compositions détergentes, parties constituantes et leurs procédés de préparation
US5178798A (en) 1989-06-09 1993-01-12 The Procter & Gamble Company Formation of detergent granules by deagglomeration of detergent dough
EP0438320A2 (fr) * 1990-01-19 1991-07-24 Unilever Plc Compositions détergentes et leur procédÀ© de préparation
WO1992006170A1 (fr) * 1990-10-03 1992-04-16 The Procter & Gamble Company Procede de preparation de compositions detersives de haute densite contenant un agent tensio-actif particulaire sensible au ph
WO1994007990A1 (fr) 1992-09-30 1994-04-14 Henkel Kommanditgesellschaft Auf Aktien Procede de fabrication de granules tensioactifs
US5482646A (en) 1993-03-05 1996-01-09 Church & Dwight Co., Inc. Powder detergent composition for cold water laundering of fabrics
EP0936269A1 (fr) * 1996-09-06 1999-08-18 Kao Corporation Particules detergentes, procede pour preparer ces particules et composition detergente presentant une masse volumique apparente importante
WO1998014557A1 (fr) 1996-10-04 1998-04-09 The Procter & Gamble Company Procede de production d'une composition detergente sans l'utilisation d'une tour
WO1999003964A1 (fr) 1997-07-14 1999-01-28 The Procter & Gamble Company Procede de production d'une composition detergente de faible densite par agglomeration controlee dans un sechoir a lit fluide
WO2000017304A1 (fr) * 1998-09-18 2000-03-30 The Procter & Gamble Company Procede en continu de fabrication d'une composition de detergent
EP1165735B1 (fr) 1999-03-30 2005-10-26 Unilever Plc Composition detergente en poudre
WO2002024854A1 (fr) * 2000-09-25 2002-03-28 Unilever Plc Production de granules de tensioactif anionique par neutralisation in situ
EP1534812B1 (fr) * 2002-09-06 2007-08-15 Kao Corporation Particules de detergent
WO2006081930A1 (fr) 2005-02-01 2006-08-10 Unilever Plc Materiau support au carbonate de sodium modifie
WO2009141203A1 (fr) * 2008-05-22 2009-11-26 Unilever Plc Fabrication de granulés de détergent par neutralisation à sec

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J. AM. CHEM. SOC., vol. 60, 1938, pages 309

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023025685A1 (fr) 2021-08-27 2023-03-02 Unilever Ip Holdings B.V. Composition détergente

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