Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
• • 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

Definitions

• the present invention relates to particulate detergent compositions containing nonionic surfactants.
• the invention is particularly concerned with particulate detergent compositions having high bulk density.
• Nonionic surfactants have beneficial cleaning
• Nonionic surfactants having a low degree of ethoxylation, employed because of their oily soil detergency, are especially
• Nonionic surfactants for possible inclusion in such powders may include some highly branched materials, as for example in EP 513 824A (Kao), EP 342 043A (Procter & Gamble) and
• EP 364 881A (Henkel).
• branched nonionic surfactants or specific disclosure of their use, in high bulk density powder in the prior art is known.
• the present invention accordingly provides a particulate detergent composition having a bulk density of at least
• a surfactant system comprising a nonionic surfactant, at least one detergency builder and optionally other detergent ingredients
• the nonionic surfactant comprises a branched-chain nonionic surfactant which is an ethoxylated C 8 -C 15 aliphatic alcohol having a degree of chain branching (defined herein as the weight% of the alcohol constituted by branched material) of at least
• the surfactant system is substantially free of ethoxylated alcohol nonionic surfactants having a degree of chain branching of less than 40 wt% and a degree of
• the invention further provides the use of a
• branched-chain nonionic surfactant which is an ethoxylated C 8 -C 15 aliphatic alcohol having a degree of chain branching of at least 40 wt% (based on the alcohol) and having an average degree of ethoxylation of from 2 to 6, to improve the
• detergent composition having a bulk density of at least
• the detergent compositions of the invention are:
• compositions of the invention is suitably from 5 to 50 wt%.
• surfactant in the compositions of the invention is suitably from 5 to 50 wt%.
• high-performance compositions containing relatively high levels of surfactant preferably from 10 to 50 wt% and more preferably from 15 to 50 wt%.
• the branched-chain nonionic surfactant has a degree of branching of at least 40 wt%, preferably at least 50 wt%.
• the degree of branching is defined here as the weight
• a degree of branching of up to 100 wt% is in principle acceptable, provided that no quaternary carbon atoms are present, but for environmental reasons a degree of branching not exceeding 70 wt% is generally preferred.
• a preferred range for the degree of branching is from 45 to 70 wt%.
• the carbon atoms (of the alcohol) are located on side chains.
• Side chains are defined as all chains other than the main chain, which is defined as the longest chain identifiable in the molecule.
• the degree of ethoxylation of the branched-chain nonionic surfactant is from 2 to 6, preferably from 2.5 to 4.
• branched-chain nonionic surfactant may have an alkyl chain length of less than C 12 , preferably from C 9 to C 11 .5 , as described and claimed in our copending application of even date, claiming priority from
• the level of free alcohol in the nonionic surfactant is less than 5 wt%, more preferably less than 1 wt%.
• Branched-chain nonionic surfactants suitable for use in the present invention include the commercially available materials listed in Table 1. (* denotes Trade Mark).
• low-ethoxylated nonionic surfactants examples include those listed in Table 2.
• low-ethoxylated (2-6EO) nonionic surfactants which are less highly branched are excluded from the compositions of the invention.
• Nonionic surfactants having a higher degree of ethoxylation may, however, be additionally present. This is advantageous from the point of view of detergency. These may be either highly branched (at least 40 wt%) or less highly branched (less than 40 wt%), the use of either being within the scope of the invention.
• a preferred nonionic surfactant system in compositions of the invention therefore comprises:
• ethoxylated C 8 -C 15 aliphatic alcohol having a degree of chain branching of at least 40 wt% and having an average degree of ethoxylation of from 2 to 6, and
• a nonionic surfactant which is an ethoxylated C 8 -C 15 aliphatic alcohol having an average degree of ethoxylation of from 6.5 to 10, preferably from 6.5 to 8.
• nonionic surfactants of higher ethoxylation and higher branching within the definition (b) which may be used in the compositions of the invention include the
• compositions of the invention therefore comprises:
• ethoxylated C 8 -C 15 aliphatic alcohol having a degree of chain branching of at least 40 wt% and having an average degree of ethoxylation of from 2 to 6, and (b) a nonionic surfactant which is an ethoxylated C 8 -C 15 aliphatic alcohol having a degree of chain branching of less than 40 wt% and having an average degree of ethoxylation of from 6.5 to 10, preferably from 6.5 to 8.
• nonionic surfactants within the definition (b) include the higher-ethoxylated analogues of the less branched materials listed in Table 2 above, for example, Synperonic A7, Lorodac LS 7L, Dobanol 23-7, Dobanol 25-7.
• Nonionic detergent-active compounds are suitably present in the compositions of the invention in a total amount of from 2 to 50 wt%, preferably from 5 to 30 wt%.
• surfactants of the class specifically excluded above are absent, other detergent-active materials may be present in the compositions of the invention.
• Detergent-active material present other than the nonionic surfactants may be other anionic (soap or non-soap), cationic, zwitterionic, amphoteric, or any combination of these.
• Anionic detergent-active compounds may be present in an amount of from 0 to 40 wt%, preferably from 0 to 20 wt%. It is preferred if the ratio of nonionic surfactant to anionic surfactant is within the range of 2:8 to 9:1.
• Synthetic anionic surfactants are well known to those skilled in the art. Examples include alkylbenzene
• sulphonates having an alkyl chain length of C 8 -C 15 ; primary and secondary alkyl sulphates, particularly sodium C 12 -C 15 primary alcohol sulphates, olefin sulphonates; alkane
• soaps of fatty acids are preferably sodium soaps derived from naturally occurring fatty acids, for example, the fatty acids from coconut oil, beef tallow, sunflower or hardened rapeseed oil.
• compositions in accordance with the invention have surfactant systems consisting essentially of branched-chain ethoxylated nonionic surfactant as defined above in combination with linear alkylbenzene sulphonate (LAS) or primary alcohol sulphate (PAS) or both.
• LAS linear alkylbenzene sulphonate
• PAS primary alcohol sulphate
• the detergent powders of the invention contain one or more detergency builders, suitably in an amount of from 5 to 80 wt%, preferably from 20 to 60 wt%.
• the invention is especially applicable to compositions containing alkali metal aluminosilicates as builders.
• Alkali metal (preferably sodium) aluminosilicates may generally be incorporated in amounts of from 5 to 60% by weight (anhydrous basis) of the composition, preferably from 25 to 55 wt%, and suitably, in a heavy duty detergent
• composition from 25 to 48 wt%.
• the alkali metal aluminosilicate may be either
• the preferred sodium aluminosilicates contain 1.5-3.5 SiO 2 units (in the formula above). Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply
• Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in
• aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof.
• the zeolite may be the commercially available zeolite 4A now widely used in laundry detergent powders.
• the zeolite builder incorporated in the compositions of the invention is maximum aluminium zeolite p (zeolite MAP) as described and claimed in EP 384 070A
• Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, and more preferably within the range of from 0.90 to 1.20.
• zeolite MAP having a silicon to aluminium ratio not exceeding 1.07.
• the calcium binding capacity of zeolite MAP is generally at least 150 mg CaO per g of anhydrous material.
• Inorganic builders that may be present include sodium carbonate, if desired in combination with a crystallisation seed for calcium carbonate, as disclosed in GB 1 437 950 (Unilever).
• Organic builders that may be present 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, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts. This list is not intended to be exhaustive.
• Builders both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.
• 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 1 to 10 wt%; and monomeric polycarboxylates, more especially citric acid and its salts, suitably used in amounts of from 3 to 35 wt%, more preferably from 5 to 30 wt%.
• compositions of the invention preferably do not contain more than 5 wt% of inorganic phosphate builders, and are desirably substantially free of phosphate builders.
• compositions in accordance with the invention may contain alkali metal, preferably sodium, carbonate, to
• Sodium carbonate may generally be present in amounts ranging from 1 to 60 wt%, preferably from 2 to 40 wt%, and most suitably from 2 to
• compositions free of alkali metal carbonate are also within the scope of the invention.
• Fully formulated laundry detergent compositions in accordance with the present invention may additionally contain any suitable ingredients normally encountered, for example, inorganic salts such as sodium silicate or sodium sulphate; organic salts such as sodium citrate; antiredeposition aids such as cellulose derivatives and acrylate or acrylate/maleate polymers; fluorescers; bleaches, bleach precursors and bleach stabilisers; proteolytic and lipolytic enzymes; dyes; coloured speckles; perfumes; foam controllers; fabric softening compounds.
• inorganic salts such as sodium silicate or sodium sulphate
• organic salts such as sodium citrate
• antiredeposition aids such as cellulose derivatives and acrylate or acrylate/maleate polymers
• fluorescers bleaches, bleach precursors and bleach stabilisers
• proteolytic and lipolytic enzymes such as cellulose derivatives and acrylate or acrylate/maleate polymers
• fluorescers bleaches, bleach precursors and bleach stabilisers
• the particulate detergent compositions of the invention may in principle be prepared by any of the available tower (spray-drying), non-tower (granulation) or combination
• compositions of high bulk density - at least 600 g/l, preferably at least 700 g/l and more preferably at least 800 g/l - which may be prepared by granulation and/or densification in a high-speed
• the high-speed mixer/granulator also known as a
• high-speed mixer/densifier may be a batch machine such as the Fukae (Trade Mark) FS, or a continuous machine such as the LOdige (Trade Mark) Recycler CB30. Suitable processes are described, for example, in EP 340 013A, EP 367 339A,
• EP 390 251A, EP 420 417A and EP 506 184A (Unilever).
• One suitable method comprises spray-drying a slurry of compatible heat-insensitive ingredients, including zeolite and any other builders, and at least part of the detergent-active compounds: densifying the resulting base powder in a batch or continuous high-speed mixer/granulator; and then spraying on or postdosing those ingredients, for example, bleach, enzymes, unsuitable for processing via the slurry.
• compatible heat-insensitive ingredients including zeolite and any other builders, and at least part of the detergent-active compounds: densifying the resulting base powder in a batch or continuous high-speed mixer/granulator; and then spraying on or postdosing those ingredients, for example, bleach, enzymes, unsuitable for processing via the slurry.
• the spray-drying step can be omitted altogether, a high bulk density base powder being prepared directly from its constituent raw materials, by mixing and granulating in a high-speed mixer/granulator, and then
• the inorganic builders and other inorganic materials are those inorganic builders and other inorganic materials (for example, zeolite, sodium carbonate).
• bleach ingredients (bleaches, bleach precursor, bleach stabilisers), proteolytic and lipolytic enzymes, coloured speckles, perfumes and foam control granules are most suitably admixed (postdosed) to the dense granular product after it has left the high-speed mixer/granulator.
• Nonionic surfactants of higher ethoxylation may be included in the base powder, post-added, or both.
• Preferably at least a part of any higher-ethoxylated nonionic surfactant is included in the base powder, while either low-ethoxylated surfactant alone or a mixture of higher- and low-ethoxylated nonionic surfactant is post-added.
• Particulate detergent compositions were prepared by spray-drying aqueous slurries to form base powders (including nonionic surfactants as specified), densifying the base powder in a continuous LfJdige high-speed mixer/granulator, spraying on further nonionic surfactants as specified, and then
• the powders had bulk densities above 700 g/litre.
• nonionic surfactants used were as shown in Table 4, Details of all these materials are given earlier in this specification.
• Test 1 The powders were compared using two different tests . Test 2
• the delivery device was attached in an upright position (opening uppermost) to an agitator arm positioned above water.
• the device could be moved vertically up and down through a distance of 30 cm, the lowest 5 cm of this travel being under water.
• Each up or down journey had a duration of 2 seconds, the device being allowed to rest 5 cm under water for 4 seconds at the lowest position, and at the highest position being rotated through 100° and allowed to rest in the
• a preweighed powder sample was introduced into the device in its highest position, and the apparatus then allowed to operate for six cycles and stopped when the device was again in its highest position. Surface water was carefully poured off, and any powder residues transferred to a preweighed container. The container was then dried at 100°C for 24 hours, and the weight of dried residue as a percentage of the initial powder weight calculated.
• Test 2 powders were also compared by means of a washing machi est.
• the machine used was a Siemens Siwamat (Trade Mark) Plus 3700 front-loading automatic washer and the test methodology was as follows.
• a 100 g dose of powder was placed in a flexible delivery device as described previously.
• the delivery device was placed inside a black cotton pillowcase having dimensions of 30 cm by 60 cm, taking care to keep it upright, and the pillowcase was then closed by means of a zip fastener.
• the pillowcase containing the (upright) delivery device was then placed on top of a 3.5 kg dry cotton washload in the drum of the washing machine.
• the machine was operated on the "heavy duty cycle" at a wash temperature of 60°C, using water of 15° French hardness and an inlet temperature of 20°C.
• a score of 3 corresponds to a residue of approximately 75 wt% of the powder, while 1
• a washing machine test was also carried out to compare the detergencies of the compositions of Examples A, B, C (comparative) and 1 and 2 (in accordance with the invention).
• the machine was again a Siemens Siwamat. 3 kg loads containing WFK-10C test cloth monitors (cotton soiled with a mixed fatty and particulate soil: wool fat and kaolin) were washed at 20°C using the half load main wash cycle.
• the powder samples 80 g dose
• Detergency results reflectance increases at 460 nm of the test cloth monitors) were as follows:
• the powders were prepared as follows. In each case, the base powder was prepared by granulation with in-situ
• Nonionic surfactant is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-N-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N
• SCMC 1.02 1.02
• the nonionic surfactants were as follows: Ex. Nonionic Chain length Branching EO E Lorodac 7 coconut (C 12-16 ) none 7EO
• the dispersion test was carried out as follows. An 0.3 g sample of powder was placed in a small spoon and wetted by holding the spoon horizontally in water at 10°C for 1 minute. The spoon was then removed and surplus water poured off. The spoon with the damp powder was then placed
• Turbidity as indicator of the dispersion of the zeolite was measured as a function of time.
• the 90% dispersion times were as follows:
• oily soil detergencies percentage removal of radio-labelled triolein soil from polyester
• surfactant systems containing cocoPAS (30 parts) and different nonionic surfactants (70 parts) having similar degrees of ethoxylation were compared in the tergotometer using a 5 g/l product concentration, 24° (French) hard water, and a wash temperature of 20°C.
• compositions were prepared to the following general formulation, nonionic surfactants and detergencies being shown in the table below:
• compositions were prepared to the following general formulation, nonionic surfactants and detergencies being shown in the table below:

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

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Cited By (15)

Citations (5)

• 1993
  • 1993-11-15 DE DE69316918T patent/DE69316918T2/de not_active Revoked
  • 1993-11-15 WO PCT/GB1993/002346 patent/WO1994011488A1/en not_active Application Discontinuation
  • 1993-11-15 ES ES93924769T patent/ES2111778T3/es not_active Expired - Lifetime
  • 1993-11-15 AU AU54313/94A patent/AU5431394A/en not_active Abandoned
  • 1993-11-15 EP EP93924769A patent/EP0670888B1/de not_active Revoked
  • 1993-11-15 JP JP6511872A patent/JPH08503241A/ja active Pending

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