WO2011061044A1 - Granulés de détergent - Google Patents

Granulés de détergent Download PDF

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Publication number
WO2011061044A1
WO2011061044A1 PCT/EP2010/066156 EP2010066156W WO2011061044A1 WO 2011061044 A1 WO2011061044 A1 WO 2011061044A1 EP 2010066156 W EP2010066156 W EP 2010066156W WO 2011061044 A1 WO2011061044 A1 WO 2011061044A1
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WO
WIPO (PCT)
Prior art keywords
sodium carbonate
las
detergent
surfactant
habit modified
Prior art date
Application number
PCT/EP2010/066156
Other languages
English (en)
Inventor
Andrew Paul Chapple
Ian Eric Niven
Original Assignee
Unilever Nv
Unilever Plc
Hindustan Unilever Limited
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 Nv, Unilever Plc, Hindustan Unilever Limited filed Critical Unilever Nv
Publication of WO2011061044A1 publication Critical patent/WO2011061044A1/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
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic 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
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • This invention relates to detergent granules comprising sodium carbonate and a mixed surfactant system including linear alkylbenzene sulphonate and nonionic surfactant.
  • PCT/EP2009/054757 relates to a process for the manufacture of detergent granules comprising anionic non-soap surfactant, the process comprising the step of dry neutralisation of surfactant acid with habit modified Sodium Carbonate, which is a crystal growth modified Sodium Carbonate that comprises a mixture of Sodium Carbonate and polymer.
  • compositions obtainable by the process in particular high active detergent granules
  • anionic surfactant comprising a major part of non-soap anionic surfactant
  • habit modified Sodium Carbonate which is a crystal growth modified Sodium Carbonate that comprises a mixture of Sodium Carbonate and polymer
  • Granular laundry detergent compositions typically contain high levels of at least 10 wt% and usually more than 20 wt ⁇ 6 or even 30 wt% of zeolite and/or phosphate builder. These builders are not considered to be environmentally desirable for future laundry detergent compositions. The problem is to obtain new compositions which are stable and effective in the absence of these materials and which can be produced using equipment suitable for commercial scale operation. It is known that selection of certain surfactant blends gives rise to Calcium tolerance. In practice, this means that a composition with little or no builder will still provide satisfactory cleaning in the presence of hard water. Calcium tolerant formulations based on LAS (linear alkylbenzene
  • the formulator will mix the LAS with a minor part of one or more co surfactants that significantly boost the ability of the surfactant system to give effective detergency in hard water without high levels of zeolite, phosphate, or even silicate builder in hard water.
  • compositions include those using specific ratios of LAS to nonionic surfactant.
  • the problem has been that to include significant total levels of surfactant in such
  • compositions it has been found necessary to provide some form of carrier material, or to process the composition in a special way, to avoid lack of storage stability due to stickiness and caking and subsequent loss of flowability of the powder
  • EP-A-420317 discloses a process for the continuous preparation of a granular detergent composition or component having a bulk density of at least 550 g/1, which comprises (i) feeding a liquid acid precursor of an anionic surfactant, a solid water- soluble alkaline inorganic material and optionally other materials into a high-speed mixer/densifier, the mean residence time being from about 5 to 30 seconds; (ii) subsequently treating the granular detergent material in a moderate-speed granulator/densifier, whereby it is brought into or maintained in a deformable state, the mean residence time being from about 1-10, preferably from 2-5 minutes; and finally (iii) drying and/or cooling the product.
  • the solid water-soluble alkaline inorganic material may comprise sodium carbonate. This process is especially useful for producing compositions comprising alky
  • the final high bulk density detergent product may for example comprise 5 to 60 wt percent of a builder, 5 to 25 wt percent carbonate, 5 to 40 wt percent anionic surfactant, 0 to 20 wt percent nonionic surfactant and 0 to 5 wt percent soap.
  • EP-A-438 320 describes a batch process for the preparation of detergent powder of high bulk density.
  • the process comprises neutralising a detergent acid (anionic surfactant precursor) , e.g. linear alkylbenzene sulphonic acid, with a particulate solid water-soluble alkaline inorganic material, for example Sodium Carbonate (optionally plus other alkaline materials and/or detergency builders, for example alkali metal
  • aluminosilicate in a high-speed mixer/granulator, e.g. Fukae mixer, and granulating the product in the mixer.
  • the reaction mixture remains particulate throughout the process, without the need to keep the temperature during the neutralisation step to 55°C or below, and a high-quality high-bulk-density particulate product is obtained.
  • Nonionic surfactants that may be present include primary and secondary alcohol ethoxylates.
  • the solids present during neutralisation may also include any other desired solid
  • ingredients for example, fluorescers ; polycarboxylate
  • compositions made all contain high levels of zeolite.
  • GB-A-1 369 269 discloses a process for the neutralisation of synthetic organic anionic detergent acids, such as straight chain alkyl benzene sulphonic acid, by mixing the acid with an excess of powdered Sodium Carbonate in a modified mixer with a cutting arrangement, for example a Lodige ploughshare mixer.
  • a builder and/or filler salt is taught to be added with the
  • Examples 1 and 2 include Sodium
  • Example 3 uses no Sodium Tripolyphosphate but the product requires pulverisation and is not described as free flowing. It is now desirable to exclude phosphate from
  • GB-A-2 221 695 describes a dry neutralisation process for preparation of detergent powder of high bulk density in a high speed mixer granulator, with a stirring and a cutting action.
  • zeolite or Sodium Tripolyphosphate is used in addition to Sodium Carbonate.
  • very high levels of Sodium Carbonate are used and a special calcite flow aid is dosed at 4% to assist with the granulation.
  • a special calcite flow aid is dosed at 4% to assist with the granulation.
  • the flow properties of example 26 are very poor and addition of Sodium Tripolyphosphate is taught as a remedy for this problem.
  • a problem with this process is that the use of a flow aid is a major process complication and it is now desirable to exclude phosphate from the granule.
  • WO 2002/24854 describes a dry neutralisation process carried out in a horizontal thin-film evaporator drier. Use of small particle size Sodium Carbonate is taught to reduce the amount of unneutralised surfactant acid in the resulting product. Such unneutralised material is known to be undesirable as it
  • zeolite is also added. This addition would reduce the level of anionic surfactant in the detergent granule. Furthermore, it is now desirable to be able to
  • US-A-7 053 038 describes a dry neutralisation process carried out in a gas fluidisation granulator using small particle size Sodium Carbonate and an inorganic acid, such as sulphuric acid. Both zeolite and sodium tripolyphosphate are included in all the examples.
  • EP-A-1 534 812 discloses dry neutralisation of preformed spray dried particles comprising a carbonate salt and polyacrylate .
  • the process is carried out under low shear conditions in order to avoid agglomeration.
  • the carbonate salt is the Burkeite double salt formed when Sodium Carbonate and sodium sulphate are spray dried together in a specified ratio. These particles are too strong to be used in the process of the present invention. As further explained later this process does not make habit modified Sodium Carbonate.
  • EP-A-221 776 describes a process to spray dry Sodium Carbonate and a crystal growth modifier to make, so called, habit modified carbonate granules.
  • the crystal growth modifier is preferably polymeric polycarboxylate .
  • the patent describes the manufacture of habit modified Burkeite in the majority of the examples. Only example 1 crystal habit modifies Sodium
  • habit modified Sodium Carbonate is a term used to encompass such prior art materials.
  • the term does not include habit modified Burkeite, although low
  • a detergent granule comprising:
  • At least 20wt% habit modified Sodium Carbonate which is a crystal growth modified Sodium Carbonate that comprises a mixture of Sodium Carbonate and polymer
  • SCMC Sodium carboxymethyl cellulose
  • the detergent granule with the NI being an alkyl ethoxylate with a degree of ethoxylation of from 25EO to 35EO, preferably 30EO and the granule comprising (wt%) :
  • the detergent granule can be made using a NI which is an alkyl ethoxylate with a degree of ethoxylation of from 5EO to 9EO and the granule comprises (wt %) :
  • HMC 20 - 67 preferably 56 - 57
  • the ratio of LAS:NI preferably lying in the range 80:20 to 70:30.
  • the granules may further comprise perfume, soap, fluorescer,
  • Granules that comprise less than 2wt% silicate are preferred, even more preferred are silicate free granules.
  • a liquids: solids ratio of 0.3 to 0.4 produces excellent detergent granules, i.e. non-dusty, granular, and of acceptabl size and dissolution rate.
  • Detergent granules having a total detergent active level from 25wt% to 45wt% with levels of habit modified sodium carbonate in excess of 20wt% may be produced stably for the first time by suitable adaptations of the process described in
  • LAS/non-ionic 25-35EO preferably 30EO systems are effective at preventing surfactant loss by precipitation.
  • the 30EO acts as a lime soap dispersant.
  • the large wedge-shaped molecules disrupt the lamellae of CaLAS, and prevent precipitation.
  • a 85/15 to 80/20 mix prevents precipitation across the entire range of water hardness, whereas a 90/10 blend will protect in soft water. If these surfactant systems produce insufficient lather for handwash, then other anionic surfactants, such as SLES, may be used in place of some or all of the highly ethoxylated
  • 7EO non-ionic may also be used; it acts primarily by reducing the cmc of the surfactant blend, thereby reducing the level of LAS monomer. It is less weight-effective at preventing
  • the 30EO nonionic is preferred over the 7EO nonionic.
  • co-surfactants such as SLES and MES, also confer Ca tolerance when blended with LAS, but again, tend to be less weight-effective than high EO non-ionic.
  • compositions are modified to take into account that a LAS/co-active ratio of between 80/20 and 70/30 is required to give Ca tolerance.
  • the product may be formulated for use only in the handwash and TL machines. This means that a 85/15 ratio to confer Ca tolerance under all conditions is preferred. This will confer a lather level closer to that traditionally seen in the handwash:
  • composition preferably comprises from 20 wt% to 70 wt% habit modified carbonate, more preferably 33 wt% to 70 wt%
  • the habit modified carbonate is used in admixture with habit modified Burkeite and then the level of habit modified carbonate may be dropped to be at the lower end of the range of at least 20 wt%, preferably at least 30 wt%.
  • Sodium Carbonate which comprises a mixture of Sodium Carbonate and polymer. Its manufacture is, for example, described in EP- A-221 776 and WO 2006/081930. It is not the same thing as habit modified Burkeite; the double salt of Sodium Carbonate and Sodium Sulphate.
  • 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
  • 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.
  • 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 . If 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 .
  • Habit modified Sodium Carbonate herein also referred to as HMC
  • HMC may be made by spray drying, as described in EP-A-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. Polycarboxylate crystal growth modifiers having molecular weights in the 3000 to 100 000 range, especially 3500 to 70 000 and more especially 10 000 to 70 000 are preferred. All
  • Preferred crystal growth modifiers are homopolymers and
  • copolymers of acrylic acid or maleic acid are polyacrylates and acrylic acid/maleic acid copolymers.
  • 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 (Trade Mark) LD 30 and 34 ex National Adhesives and Resins Ltd, average molecular weights 5000 and 25 000
  • copolymers for example, the EMA (Trade Mark) series ex
  • a second group of polymeric crystal growth modifiers comprises polyaspartic acids and polyaspartates .
  • Preferred polymeric crystal growth modifiers in this second group have a molecular weight of at least 1000, advantageously from 3500 to 300000, especially from 4000 to 250000.
  • HMC is preferably prepared using polyaspartate crystal growth
  • 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
  • the Sodium Carbonate used to make the habit modified Sodium 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.
  • surfactant acids include alpha-olefin sulphonic acids, internal olefin sulphonic acids, fatty acid ester sulphonic acids and primary sulphonic acids.
  • Soaps formed by the dry neutralisation of carboxylic or fatty acids may be used as secondary anionic surfactants in admixture with the non-soap anionic surfactants.
  • Preferred carboxylic acids are fatty acids with 12-18 carbon atoms, such as for example fatty acids of coconut oil, palm oil, palm kernel and tallow.
  • the fatty acids may be saturated or unsaturated, branched or straight chain. Mixtures of fatty acids may be used.
  • Fatty acids may be used at levels of up to 30 wt% based on the surfactant acid.
  • 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.
  • the detergent granules also comprise a conventional level of this polymer. Its inclusion adds strength to the granule during processing and it also confers benefits to the detergent composition .
  • 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) . As discussed already neutralised anionic surfactant may be mixed with the surfactant 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 . 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
  • Calcium tolerant surfactant blends that may be dry neutralised include mixtures of LAS with nonionic high EO, SLES paste and/or AOS paste.
  • 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.
  • 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.
  • neutralised paste surfactants are preferably added after the completion of neutralisation.
  • the surfactant acid is preferably used in liquid form and advantageously it is reacted while mixing with a molar excess of habit modified Sodium Carbonate to form a sodium salt of the anionic surfactant, while mixing.
  • a molar excess of habit modified Sodium Carbonate the reaction may be done with a mixture of habit modified Sodium Carbonate and a smaller amount of other conventional Sodium Carbonate, such as light ash and/or Burkeite, with a corresponding
  • 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 total amount of free water that can be tolerated in the process preferably should not amount to more than 8 wt% of the total composition, preferably not more than 4 wt%.
  • 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 a 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 reaction and for regranulation . Thus, a conventional fluid bed granulator would not be preferred for the dry neutralisation process using habit modified carbonate.
  • the mixing is carried out in a mixer having and using both a stirring action and a cutting action, most preferably these actions will be separately usable, as
  • 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 stirring action and a cutting action.
  • the highspeed mixer/granulator has rotatable stirrer and cutter elements that can be operated independently of one another, and at separately changeable or variable speeds.
  • 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.
  • mixers of the Fukae FS-G type manufactured by Fukae Powtech Co Ltd., Japan are also preferred; 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.
  • 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 has excellent flow properties, low compressibility and little tendency towards caking.
  • the particulate detergent granules that are the direct result of the dry neutralisation process have a surfactant content of 25 wt% to 45 wt%.
  • 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 high levels of surfactant in the granule without any processing difficulties or complications.
  • the inclusion of nonionic surfactant often leads to stickiness but the high carrying capacity of the excess habit modified carbonate ensures that this is not thee case for the granules of the present invention.
  • the fast reaction with the habit modified carbonate ensures that the granule becomes stable very quickly during the process and there is no concern about further neutralisation occurring which would require some sort of "aging" process.
  • 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.
  • 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 formulated powder detergent composition and to enhance the visual appearance of the powder.
  • the detergent granules may be admixed with anything normally used in detergent formulations. They 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
  • Soap may also be present, to provide foam control 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.
  • the detergent granules may be mixed with another powder
  • any conventional detergent production process including spray drying or non spray drying processes.
  • 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 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 typically, 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
  • Powder flow may be quantified by means of the dynamic flow rate (DFR), in ml/s, measured by means of the following procedure.
  • DFR dynamic flow rate
  • the apparatus used consists of a cylindrical glass tube having an internal diameter of 35 mm and a length of 600 mm. The tube is securely clamped in a position such that its longitudinal axis is vertical. Its lower end is terminated by means of a smooth cone of polyvinyl chloride having an internal angle of 15° and a lower outlet orifice of diameter 22.5 mm.
  • a first beam sensor is positioned 150 mm above the outlet, and a second beam sensor is positioned 250 mm above the first sensor.
  • the outlet orifice is temporarily closed, for example, by covering with a piece of card, and powder is poured through a funnel into the top of the cylinder until the powder level is about 10 cm higher than the upper sensor; a spacer between the funnel and the tube ensures that filling is uniform.
  • the outlet is then opened and the time t (seconds) taken for the powder level to fall from the upper sensor to the lower sensor is measured electronically. The measurement is normally repeated two or three times and an average value taken. If V is the volume (ml) of the tube between the upper and lower sensors, the dynamic flow rate DFR (ml/s) is given by the following equation:
  • the powder is loaded into a cylinder and the surface levelled.
  • a 50 g plastic disc is placed on top of the powder and a 10 kg weighted plunger is placed slowly on top of the disc and allowed to remain in position for 2 minutes.
  • the weight and plunger are then removed and the cylinder removed carefully from the powder to leave a free-standing cylinder of powder with the 50g plastic disc on top of it.
  • a second 50 g plastic disc is placed on top of the first and left for approximately ten seconds.
  • a 100 g disc is added to the plastic discs and left for ten seconds.
  • the weight is then increased in 0.25 kg increments at 10 second intervals until the compact collapses.
  • the total weight (w) needed to effect collapse is noted .
  • the cohesiveness of a powder is classified by the weight (w) as follows : w ⁇ 1.0 kg Good flowing 1.0 kg ⁇ w ⁇ 2.0 kg Moderate flowing. 2.0 kg ⁇ w ⁇ 5.0 kg Cohesive. 5.0 kg ⁇ w Very cohesive.
  • a 1-litre beaker is filled with 500mls of demineralised water at 20-25°C and stirred with a magnetic stirrer adjusted to give a vortex of about 4cm.
  • a sample of powder is added to the water.
  • the dissolution is measured according to solution conductivity.
  • the T90' value is the time taken to achieve 90% of the final conductivity value.
  • HMC was prepared according to WO 2006/081930 Al by mixing together 29.8 kg of Sokalan CP5 solution (40% active material) with 1373.8kg of water in a stirred tank. Into this solution was then dissolved 596.4 kg of light Sodium Carbonate (ex
  • Mean size about 400 microns.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne un granulé de détergent qui comprend : a) de 25 % en poids à 45 % en poids d'un tensioactif, qui comporte un acide alkylbenzènesulfonique linéaire neutralisé avec un carbonate à faciès modifié pour former un alkylbenzènesulfonate linéaire (LAS) de sodium et un tensioactif non ionique éthoxylé ayant un degré d'éthoxylation de 5 à 50 OE (tensioactif NI), le granulé présentant un rapport LAS/NI de 90:10 à 70:30, de préférence de 85:15 à 75:25, b) au moins 20 % en poids 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, et c) moins de 10 % en poids, de préférence 0 %, de zéolite, moins de 1 % en poids, de préférence 0 %, de phosphate, e) de 0,2 % en poids à 4 % en poids de carboxyméthylcellulose sodique (SCMC) que l'on peut obtenir par un procédé comprenant la neutralisation à sec d'un acide LAS liquide avec du carbonate de sodium à faciès modifié, l'acide LAS étant mis à réagir sous agitation avec un excès molaire de carbonate de sodium à faciès modifié pour former un LAS de sodium, pendant l'agitation.
PCT/EP2010/066156 2009-11-20 2010-10-26 Granulés de détergent WO2011061044A1 (fr)

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Cited By (11)

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EP2740786A1 (fr) 2012-12-06 2014-06-11 Solvay SA Procédé de préparation de particules de composition de détergent
WO2014172902A1 (fr) * 2013-04-26 2014-10-30 The Procter & Gamble Company Granules de détergent avec un composant hydro-expansible
CN105164242A (zh) * 2013-04-26 2015-12-16 宝洁公司 具有水可溶胀组分的洗涤剂颗粒
WO2015189248A1 (fr) * 2014-06-10 2015-12-17 Solvay Sa Procédé de production de particules de composition détergente
EP3075831A1 (fr) * 2015-03-30 2016-10-05 The Procter and Gamble Company Composition de detergent de blanchisserie particulaire solide a ecoulement libre
WO2017190300A1 (fr) * 2016-05-05 2017-11-09 The Procter & Gamble Company Compositions de nettoyage
US9951301B2 (en) 2015-03-30 2018-04-24 The Procter & Gamble Company Solid free-flowing particulate laundry detergent composition
US9951296B2 (en) 2015-03-30 2018-04-24 The Procter & Gamble Company Solid free-flowing particulate laundry detergent composition
US9957466B2 (en) 2015-03-30 2018-05-01 The Procter & Gamble Company Solid free-flowing particulate laundry detergent composition
US9957470B2 (en) 2015-03-30 2018-05-01 The Procter & Gamble Company Solid free-flowing particulate laundry detergent composition
US10053654B2 (en) 2015-04-02 2018-08-21 The Procter & Gamble Company Solid free-flowing particulate laundry detergent composition

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EP0221776A2 (fr) 1985-11-01 1987-05-13 Unilever Plc Compositions détergentes, parties constituantes et leurs procédés de préparation
US4692275A (en) 1986-04-23 1987-09-08 Lever Brothers Company Detergent compositions containing an alkylbenzene sulfonate and alcohol ethoxysulfate surfactant system
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EP0221776A2 (fr) 1985-11-01 1987-05-13 Unilever Plc Compositions détergentes, parties constituantes et leurs procédés de préparation
US4692275A (en) 1986-04-23 1987-09-08 Lever Brothers Company Detergent compositions containing an alkylbenzene sulfonate and alcohol ethoxysulfate surfactant system
GB2221695A (en) 1988-07-21 1990-02-14 Unilever Plc Granular detergents
EP0420317A1 (fr) 1989-09-29 1991-04-03 Unilever N.V. Procédé de préparation de compositions détergentes à haute densité apparente
WO1998020104A1 (fr) * 1996-11-06 1998-05-14 The Procter & Gamble Company Procede de neutralisation destine a la fabrication de granules agglomerees de detergent
WO2002024854A1 (fr) 2000-09-25 2002-03-28 Unilever Plc Production de granules de tensioactif anionique par neutralisation in situ
US7053038B2 (en) 2001-08-13 2006-05-30 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Process for the production of detergent granules
EP1534812A1 (fr) 2002-09-06 2005-06-01 Kao Corporation Particules de detergent
WO2006081930A1 (fr) 2005-02-01 2006-08-10 Unilever Plc Materiau support au carbonate de sodium modifie
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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2740786A1 (fr) 2012-12-06 2014-06-11 Solvay SA Procédé de préparation de particules de composition de détergent
WO2014086985A1 (fr) 2012-12-06 2014-06-12 Solvay Sa Procédé de préparation de particules de composition détergente
CN104968775A (zh) * 2012-12-06 2015-10-07 索尔维公司 用于制备洗涤剂组合物颗粒的方法
WO2014172902A1 (fr) * 2013-04-26 2014-10-30 The Procter & Gamble Company Granules de détergent avec un composant hydro-expansible
WO2014173198A1 (fr) * 2013-04-26 2014-10-30 The Procter & Gamble Company Granulés de détergent contenant un constituant pouvant gonfler dans l'eau
CN105164242A (zh) * 2013-04-26 2015-12-16 宝洁公司 具有水可溶胀组分的洗涤剂颗粒
WO2015189248A1 (fr) * 2014-06-10 2015-12-17 Solvay Sa Procédé de production de particules de composition détergente
CN106573789A (zh) * 2014-06-10 2017-04-19 索尔维公司 用于生产洗涤剂组合物颗粒的方法
WO2016160870A1 (fr) * 2015-03-30 2016-10-06 The Procter & Gamble Company Composition détergente de lavage du linge particulaire, à écoulement libre et solide
EP3075831A1 (fr) * 2015-03-30 2016-10-05 The Procter and Gamble Company Composition de detergent de blanchisserie particulaire solide a ecoulement libre
US9951301B2 (en) 2015-03-30 2018-04-24 The Procter & Gamble Company Solid free-flowing particulate laundry detergent composition
US9951296B2 (en) 2015-03-30 2018-04-24 The Procter & Gamble Company Solid free-flowing particulate laundry detergent composition
US9957466B2 (en) 2015-03-30 2018-05-01 The Procter & Gamble Company Solid free-flowing particulate laundry detergent composition
US9957470B2 (en) 2015-03-30 2018-05-01 The Procter & Gamble Company Solid free-flowing particulate laundry detergent composition
US10053654B2 (en) 2015-04-02 2018-08-21 The Procter & Gamble Company Solid free-flowing particulate laundry detergent composition
WO2017190300A1 (fr) * 2016-05-05 2017-11-09 The Procter & Gamble Company Compositions de nettoyage
CN109072140A (zh) * 2016-05-05 2018-12-21 宝洁公司 清洁组合物

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