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
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; 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
  • 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
  • C11D1/37—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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
  • C11D17/065—High-density particulate detergent compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/128—Aluminium silicates, e.g. zeolites
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • 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
• • 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

Definitions

• the present invention relates to particulate detergent compositions, particularly those of high bulk density, containing primary alcohol sulphate (PAS), built with alkali metal aluminosilicate, and optionally containing sodium carbonate.
• PAS primary alcohol sulphate
• Detergent compositions built with zeolite and containing both alkylbenzene sulphonate and PAS are disclosed in JP 62 240 397A (Kao), JP 62 273 300A (Kao), EP 219 314A (Procter & Gamble) and EP 220 024A (Procter & Gamble).
• JP 01 142 000A (Nippon Gosen Senzai) discloses a high bulk density detergent composition prepared by neutralising PAS acid with sodium carbonate and zeolite.
• EP 342 917A discloses detergent compositions containing PAS having a specific chain length distribution.
• EP 340 013A (Unilever) relates to high-bulk-density detergent powders containing a moderate to high proportion of surfactant (particularly anionic surfactant) and a relatively high proportion of zeolite builder.
• the preferred and exemplified anionic surfactant is alkylbenzene sulphonate.
• the powders are preferably prepared by processes involving granulation and densification of a spray-dried powder in a high-speed mixer/granulator having both a stirring action and a cutting action.
• the present invention is based on the observation that, in detergent compositions of the general type disclosed in EP 340 013A (Unilever), when PAS is used partially or wholly in place of alkylbenzene sulphonate, surprisingly improved detergency can be achieved by adjustment of the amount of sodium carbonate present.
• the present invention accordingly provides a particulate detergent composition which comprises:
• the subject of the invention is a detergent composition in particulate form characterised by a moderate to high content of anionic surfactant, including or consisting of primary alcohol sulphate; a relatively high level of aluminosilicate builder; and a suitably chosen level of sodium carbonate ranging from zero to moderately high.
• anionic surfactant including or consisting of primary alcohol sulphate; a relatively high level of aluminosilicate builder; and a suitably chosen level of sodium carbonate ranging from zero to moderately high.
• the weight ratio of aluminosilicate builder (c) to total non-soap surfactant (a) is within the range of from 0.9:1 to 2.6:1, more preferably from 1.2:1 to 1.8:1.
• the detergent composition of the invention comprises from 17 to 35 wt% of non-soap detergent-active material, of which a specified anionic surfactant component is an essential ingredient.
• the specified anionic surfactant component which constitutes from 5 to 35 wt% of the whole composition, consists either of primary alcohol sulphate (PAS) alone, or of PAS in admixture with linear alkylbenzene sulphonate (LAS). If both LAS and PAS are present, PAS must constitute at least 10 wt%, and preferably at least 20 wt%, of the two together, while LAS can constitute up to 90 wt%, and preferably up to 80 wt%, of the two together.
• PAS primary alcohol sulphate
• LAS linear alkylbenzene sulphonate
• the amount of LAS present and the relative proportions of LAS and PAS determine the amount of sodium carbonate, if any, present.
• An essential ingredient of the surfactant system is a primary alcohol sulphate (PAS), also known as alkyl sulphate.
• PAS constitutes from 10 to 100 wt% of the essential anionic surfactant component in the compositions of the invention, which itself constitutes from 5 to 35 wt% of the whole composition.
• anionic surfactants have received much attention recently as potential replacements for alkylbenzene sulphonates on environmental grounds, but have shown some deficiencies in all-round detergency performance under a wide range of wash conditions.
• Alcohol sulphates may be derived from both synthetic and natural alcohols containing from about 8 to 22 carbon atoms.
• suitable alcohols that can be used for PAS manufacture include decyl, lauryl, myristyl, palmityl and stearyl alcohols, and the mixture of fatty alcohols derived by reducing the glycerides of tallow and coconut oils.
• Natural alcohols, for example, tallow or coconut alcohol give rise to straight-chain (linear) PAS, while synthetic alcohols, for example those produced by the Oxo process, can give rise to either linear or branched-chain PAS. Both linear and branched PAS are suitable for use in the present invention.
• PAS is a mixture containing a spread of chain lengths.
• the PAS used in the compositions of the present invention is preferably of relatively short chain length, that is to say, it consists wholly or predominantly of material having an alkyl chain length of C16 or below, and more preferably consists wholly or predominantly of material having an alkyl chain length of C14 or below.
• Short-chain PAS is especially suitable for products intended solely or predominantly for low-temperature ( ⁇ 25°C) washing conditions.
• Preferred PAS of natural origin is derived from coconut oil, palm kernel oil, babassu oil, or macauba oil.
• coconut alcohol PAS (cocoPAS), either as the natural material consisting predominantly of linear C12 and C14 alcohols with smaller amounts of shorter- and longer-chain material, or as a "narrow-cut” material enriched in C12 and C14 alcohols by fractionation. CocoPAS exhibits good low-temperature detergency, is of renewable natural origin, and is biodegradable.
• longer-chain PAS such as tallow PAS is preferably absent, or present in a relatively low proportion, because its low-temperature performance is poor.
• the main anionic surfactant component which constitutes 5 to 35 wt% of the composition, may comprise linear alkylbenzene sulphonate (LAS) in addition to PAS, provided that PAS constitutes at least 10 wt%, and preferably at least 20 wt%, of the two together.
• LAS linear alkylbenzene sulphonate
• Linear alkylbenzene sulphonates are exceedingly well-known ingredients of fabric washing detergent compositions.
• the alkyl chain length is generally in the C8-C15 range.
• compositions of the invention may also contain up to 10 wt% of nonionic surfactant.
• nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the aliphatic C12-C15 primary and secondary alcohols ethoxylated with an average of from 3 to 20 moles of ethylene oxide per mole of alcohol; and alkylpolyglycosides.
• the composition may alternatively or additionally contain up to 10 wt% of one or more anionic surfactants other than LAS and PAS.
• anionic surfactants are alkyl ether sulphates, alkyl xylene sulphonates, olefin sulphonates, dialkyl sulphosuccinates and fatty acid ester sulphonates.
• the composition of the invention may contain up to 10 wt% of fatty acid soap, to provide foam control and additional detergency and builder power. Soap, if present, is not included within the total of 17 to 35 wt% which refers only to non-soap surfactant.
• the alkali metal (preferably sodium) aluminosilicate builder present in the composition of the invention may be crystalline or amorphous or a mixture thereof.
• the sodium salts have the general formula 0.8-1.5 Na2O.Al2O3.0.8-6 SiO2.
• aluminosilicates contain 1.5-3.5 SiO2 units (in the formula above) and have a particle size of not more than about 100 microns, preferably not more than about 20 microns. Both amorphous and crystalline aluminosilicates can be made readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
• Crystalline aluminosilicates are preferred for use in the present invention. Suitable materials are described, for example, in GB 1 473 201 (Henkel) and GB 1 429 143 (Procter & Gamble).
• the preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof.
• Especially preferred for use in the present invention is Type 4A zeolite.
• the aluminosilicate detergency builder is present in an amount of from 25 to 45 wt% (anhydrous basis), and preferably at the relatively high level of 28 to 45 wt%. This has been found to give processing advantages for high-bulk-density compositions (see below) as well as good cleaning performance.
• a supplementary builder may also be present.
• Preferred supplementary builders are organic sequestrant builders. Examples include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates.
• organic precipitant builders such as alkyl- and alkenylmalonates and succinates, and sulphonated fatty acid salts, may be used.
• Especially preferred supplementary builders are polycarboxylate polymers, more especially polyacrylates and acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, especially from to 10 wt%; and monomeric polycarboxylates, more especially citric acid and its salts, suitably used in amounts of from 3 to 20 wt%, more preferably from 5 to 15 wt%.
• composition of the invention preferably does not contain more than 5 wt% of inorganic phosphate builders, and is desirably substantially free of phosphate builders.
• the amount of sodium carbonate present is a key feature of the invention.
• the composition of the invention contains, as an essential ingredient, sodium carbonate in an amount of from 10 to 20 wt%. It has surprisingly been found that the presence of sodium carbonate at this level gives a detergency advantage over similar compositions containing lower amounts of, or no, carbonate; while the amount of carbonate has no significant effect on a similar LAS-only system.
• the main anionic surfactant component (a)(i) consists of 10-60 wt% PAS and 40-90 wt% LAS, the amount of carbonate should be low or zero -from 0 to 10 wt% - for optimum detergency.
• a preferred anionic surfactant component within this area, where low carbonate is preferred comprises 20-50 wt% PAS and 50-80 wt% LAS, more preferably 30-40 wt% PAS and 60-70 wt% LAS.
• the amount of carbonate appears to have a less marked effect on the detergency and can therefore range from nil to 20 wt%.
• a low carbonate level of nil to 10 wt% is preferred, especially at 60-75 wt% PAS and 25-40 wt% LAS.
• the composition has a bulk density of least 650 g/litre, more preferably at least 700 g/litre.
• Particle porosity preferably does not exceed 0.25, and more preferably does not exceed 0.20.
• High-bulk-density compositions in accordance with the invention may be prepared by a variety of processes, batch or continuous, some involving post-tower densification of a spray-dried powder, and others involving wholly non-tower processing.
• One type of process involves subjecting a particulate starting material (in effect, a particulate detergent of conventional bulk density) to a granulation/densification treatment.
• the starting material may itself be prepared by spray-drying or by a non-tower process such as dry mixing or granulation.
• This treatment may be carried out in a high-speed batch mixer/granulator having both a stirring action and a cutting action, as described and claimed in EP 340 013A (Unilever).
• the stirrer and the cutter may be operated independently of one another, and at separately 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. It is thus a highly versatile and flexible piece of apparatus.
• a preferred type of batch high-speed mixer/granulator is bowl-shaped and preferably has a substantially vertical stirrer axis.
• mixers of the Fukae (Trade Mark) FS-G series manufactured by Fukae Powtech Kogyo Co., Japan are 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 Fukae mixer may also be used to produce compositions of the invention directly from raw materials by high-speed mixing and granulation.
• PAS and LAS may be introduced into the mixer in, for example, powder, flake, noodle or paste form. It is also possible to use processes in which PAS or LAS or both are prepared by neutralisation in situ, for example, as described and claimed in EP 352 135A (Unilever) and in our copending European Patent Application No. 91 300 422.2.
• the Fukae mixer requires batch operation.
• continuous processes may be employed, for example, using a continuous high-speed mixer/granulator such as the Lödige (Trade Mark) Recycler, optionally followed by a moderate-speed continuous mixer/granulator such as the Lödige Ploughshare.
• this apparatus can be used for both post-tower and non-tower processes, including in-situ neutralisation. Suitable processes are disclosed in EP 367 339A, EP 390 251A and EP 420 317A (Unilever), and in our copending European Patent Application No. 91 200 740.8.
• the granulate obtained from the mixer/granulator may be used as a complete detergent composition in its own right. Alternatively, it may be admixed with other components or mixtures prepared separately, and may form a major or minor part of a final product.
• Detergent compositions in accordance with the invention may if desired or appropriate contain other functional ingredients.
• bleach ingredients, lather control agents, enzymes and perfume are more suitably added afterwards.
• the skilled detergents worker will have no difficulty in judging when and how the various ingredients that go to make up a fully formulated detergent composition should be incorporated.
• Detergent powders were prepared to the formulations shown in Tables 1 and 2.
• the PAS used was Empicol (Trade Mark) LX, a narrow-cut (C12/C14 enriched) cocoPAS (Na salt) supplied by Albright & Wilson.
• Examples 1, 2, A, B and C in Table 1 were high-carbonate compositions, and Examples D, 3, 4, 5 and E in Table 2 were zero-carbonate formulations.
• the comparative all-LAS powders C and E were prepared by spray-drying an aqueous slurry of all ingredients except sodium carbonate, sodium sulphate and enzyme, to form a common base powder; densifying the base powder using the Fukae FS-100 high-speed mixer/granulator, as described in EP 340 013A (Unilever); then admixing the relevant inorganic salt (sodium carbonate or sodium sulphate) and enzyme.
• the all-PAS powders 1 and D were prepared by dry-mixing the PAS (in powder form) with all other ingredients except sodium carbonate, sodium sulphate and enzyme to form a base, in the Fukae mixer; densifying; then admixing the relevant inorganic salt (sodium carbonate or sodium sulphate) and enzyme.
• the LAS/PAS powders (Examples 2, A, B, 3, 4 and 5) were prepared by admixing the appropriate quantities of the LAS base powder of Examples C and E and the PAS base powder of Examples 1 and D, then proceeding as in the other Examples.
• the final powders had bulk densities above 720 g/litre. They were free-flowing and showed no tendency to cake.
• Test Cloth 1 carried a mixture of fatty and particulate soil
• Test Cloth 2 a mixture of fatty soil, particulate soil and casein.
• the powders were dosed at 0.96 g/litre into 35 litres of water (5° French hard in Ca2+, 2° French hard in Mg2+) in a Japanese (National (Trade Mark) Electronic W100) washing machine; the test cloths were washed together with a 2.0 kg soiled cotton load, the wash time being 8 minutes and the rinse time also 8 minutes (running rinse).

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)

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Cited By (11)

Citations (13)

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• 1990
  • 1990-06-06 GB GB909012612A patent/GB9012612D0/en active Pending
• 1991
  • 1991-05-30 CA CA002043542A patent/CA2043542C/en not_active Expired - Fee Related
  • 1991-06-03 AU AU78111/91A patent/AU633438B2/en not_active Ceased
  • 1991-06-04 IN IN163BO1991 patent/IN172490B/en unknown
  • 1991-06-04 DE DE69129133T patent/DE69129133T3/de not_active Expired - Fee Related
  • 1991-06-04 EP EP91305058A patent/EP0460925B2/de not_active Expired - Lifetime
  • 1991-06-04 ES ES91305058T patent/ES2114877T3/es not_active Expired - Lifetime
  • 1991-06-05 KR KR1019910009288A patent/KR950008981B1/ko not_active IP Right Cessation
  • 1991-06-05 JP JP3134343A patent/JP2569237B2/ja not_active Expired - Fee Related
  • 1991-06-05 BR BR919102333A patent/BR9102333A/pt not_active IP Right Cessation
  • 1991-06-06 ZA ZA914329A patent/ZA914329B/xx unknown

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