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
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2075—Carboxylic acids-salts thereof
  • C11D3/2086—Hydroxy carboxylic acids-salts thereof
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • 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

Definitions

• the present invention relates to detergent compositions, especially particulate detergent compositions, suitable for the laundering of fabrics in domestic or commercial washing machines.
• the compositions contain a specific combination of aluminosilicate and citrate builder salts.
• Detergent compositions for heavy-duty fabric washing conventionally contain materials - detergency builders - to lower the concentration of calcium water hardness ions in the wash liquor and thus to give good detergency in hard water as well as in soft water.
• Alkali metal aluminosilicate ion-exchangers are now well-known replacements for the inorganic phosphates traditionally used as detergency builders in fabric washing detergents. It is also well known that zeolites show certain deficiencies in detergency building, as compared with phosphates, and that supplementary building power is generally desirable. In many zero-phosphate premium detergent powders now on the European market, homo- or copolymers of acrylic acid are included for this purpose.
• citric acid and/or its salts in detergent compositions, but these compounds are well-known to be poor sequestrants of calcium ions and to contribute little to detergency building.
• Detergent compositions built with crystalline aluminosilicate (zeolite) and also containing citrates are specifically disclosed in GB 1 473 201 (Henkel), GB 1 429 143 (Procter & Gamble), GB 1 470 250 (Procter & Gamble), EP 1310A (Procter & Gamble), EP 1853A (Procter & Gamble), EP 75 796B (Procter & Gamble), GB 2 095 274B (Colgate-Palmolive), DE 2 336 182C (Lion), EP 234 867A (Clorox), and also in our copending European Patent Application No. 90 311 672.1 filed on 24 October 1990.
• EP 313 143A discloses bleaching detergent compositions containing aluminosilicate (15-40 wt%), citric acid or alkali metal citrate (1-15 wt%), and a solid organic peroxyacid (1-15 wt%).
• EP 313 144A describes and claims bleaching detergent compositions containing aluminosilicate (15-40 wt%), citric acid or alkali metal citrate (1-15 wt%), an inorganic peroxy compound (5-35 wt%), and a peroxybenzoic acid bleach precursor (1-10 wt%). Both specifications claim improved cleaning and bleaching performance when a builder system based on zeolite and citrate is used in conjunction with these specific bleach systems.
• compositions of the invention can give detergency as good as that obtained from compositions built with aluminosilicate/acrylic polymer, despite the known inferiority of citrate to acrylic polymer as a binder of calcium ions.
• the present invention provides a detergent composition for fabric washing, comprising:
• the invention also provides a method of washing fabrics, which includes the step of bringing the fabrics into contact with an aqueous wash liquor containing a detergent composition as defined in the previous paragraph.
• the invention further provides the use of (x) citric acid or a salt thereof, in an amount equivalent to from 3 to 18 wt% of sodium citrate dihydrate, as a detergency builder in a detergent composition for fabric washing comprising:
• the detergent composition of the invention contains, as essential components, a detergent-active compound, and a detergency builder system.
• the detergent compositions of the invention will contain, as essential ingredients, one or more detergent-active compounds (surfactants) which may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active compounds, and mixtures thereof.
• surfactants may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active compounds, and mixtures thereof.
• suitable detergent-active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
• the preferred detergent-active compounds that can be used are soaps and synthetic non-soap anionic and nonionic compounds.
• Anionic surfactants are well-known to those skilled in the art. 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; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
• Sodium salts are generally preferred.
• 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.
• Preferred detergent-active systems suitable for compositions intended for use in automatic fabric washing machines, comprises anionic non-soap surfactant, or nonionic surfactant, or combinations of the two in any ratio, optionally together with soap.
• the total amount of detergent-active compounds present may suitably lie in the range of from 5 to 40 wt%.
• the detergency builder system comprises, and preferably consists essentially of, two components (a) and (b).
• the component (a) will be referred to hereinafter as the aluminosilicate
• the component (b) will be referred to as the citrate. All percentages of the aluminosilicate will be based on the anhydrous material, and all percentages of the citrate will be based on sodium citrate dihydrate equivalent.
• the alkali metal (preferably sodium) aluminosilicate builder may be crystalline or amorphous or a mixture thereof, and has 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 ⁇ m, preferably not more than about 20 ⁇ m. 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.
• Zeolite A more especially Type 4A zeolite, is especially preferred for use in the present invention, as described in more detail below.
• Zeolite MAP is defined as zeolite P having a silicon to aluminium ratio not exceeding 1.33, preferably from 0.9 to 1.33, more preferably from 0.9 to 1.2.
• Preferred zeolite MAP has a silicon to aluminium ratio not exceeding 1.15 and has a tetragonally distorted cubic crystal structure.
• Especially preferred zeolite MAP has a silicon to aluminium ratio not exceeding 1.07.
• Detergency builders and detergent compositions containing zeolite MAP and citrate are also the subject of our copending Application of even date (Case C3367/1) claiming the priority of British Patent Application No. 90 06171.4 filed on 19 March 1990.
• zeolites contain water of hydration, as mentioned above, for the purposes of the present invention amounts and percentages of zeolites are expressed in terms of the anhydrous material.
• the citrate is the citrate
• the second essential builder component of the compositions of the invention is citric acid or a salt thereof, preferably sodium citrate.
• This salt normally exists in the form of the dihydrate, and for the purposes of the present invention amounts and percentages of citrates are expressed in terms of sodium citrate dihydrate.
• the aluminosilicate should be present in an amount of from 18 to 45 wt% and the citrate should be present in an amount of from 3 to 18 wt%
• the weight ratio of aluminosilicate to citrate should be within the range of from 2.5:1 to 6:1.
• the detergency builder system comprises from 18 to 30 wt%, preferably from 20 to 30 wt%, more preferably from 22 to 28 wt% and most preferably from 24 to 28 wt%, of the alkali metal aluminosilicate; and from 3 to 18 wt%, preferably from 5 to 7 wt%, of the citrate.
• the aluminosilicate is preferably zeolite A or zeolite MAP.
• the total amount of aluminosilicate plus citrate is preferably from 22 to 36 wt%, preferably from 28 to 36 wt%.
• the ratio of aluminosilicate to citrate is preferably from 3:1 to 6:1, more preferably from 4:1 to 5:1.
• the first preferred embodiment of the invention is especially applicable to compositions containing a bleach system, as described below.
• the detergency builder system comprises from 35 to 45 wt%, preferably from 37 to 42 wt%, of the alkali metal aluminosilicate and from 9 to 18 wt%, preferably from 10 to 15 wt%, of the citrate.
• the aluminosilicate is preferably zeolite A.
• the total amount of aluminosilicate plus citrate is preferably from 50 to 60 wt%, and the ratio of aluminosilicate to citrate is preferably form 2.5:1 to 4.5:1.
• the second preferred embodiment of the invention is esepcially applicable to compositions that do not contain a bleach system.
• compositions of the invention may be formulated without homo- or copolymers of acrylic acid, for example, polyacrylates or acrylic/maleic copolymers. Preferred compositions are substantially free from such polymers, although compositions containing them are not excluded from the scope of the invention.
• the amount of soluble silicates in the compositions of the invention is preferably kept to a relatively low level: preferably below 5 wt%, and more preferably below 1 wt%.
• compositions of the invention may advantageously contain alkali metal carbonate, to provide alkalinity rather than for detergency building.
• alkali metal, preferably sodium, carbonate may suitably range from 2 to 20 wt%, preferably from 5 to 15 wt%.
• Detergent compositions according to the invention may also suitably contain a bleach system, provided that peroxybenzoic acid bleach precursors and solid organic peroxyacids are absent.
• the bleach system preferably comprises one or more peroxy bleach compounds, for example, inorganic persalts, which may be employed in conjunction with precursors to improve bleaching action at low wash temperatures. More preferably the bleach system comprises an inorganic persalt optionally in conjunction with a precursor other than a peroxybenzoic acid precursor.
• peroxy bleach compounds for example, inorganic persalts, which may be employed in conjunction with precursors to improve bleaching action at low wash temperatures. More preferably the bleach system comprises an inorganic persalt optionally in conjunction with a precursor other than a peroxybenzoic acid precursor.
• Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate.
• Preferred bleach precursors are peracetic acid precursors, especially tetraacetylethylene diamine (TAED), and the novel quaternary ammonium and phosphonium bleach activators disclosed in US 4 751 015 and US 4 818 426 (Lever Brothers Company), more especially cholyl p-sulphophenyl carbonate (CSPC).
• TAED tetraacetylethylene diamine
• CSPC cholyl p-sulphophenyl carbonate
• the bleach system may also include a bleach stabiliser (heavy metal sequestrant).
• a bleach stabiliser heavy metal sequestrant
• compositions containing a bleach system are preferably in accordance with the first preferred embodiment of the invention, as described above.
• the invention is especially, but not exclusively, concerned with detergent compositions in particulate form.
• Particulate compositions of the invention may advantageously contain a dicarboxylic acid powder structurant.
• Suitable materials include succinic acid, adipic acid, glutaric acid and mixtures thereof.
• the acids may be employed in free acid or in salt (wholly or partially neutralised) form.
• the dicarboxylic acid is suitably employed in an amount within the range of from 0.5 to 5 wt%.
• a commercial mixture of adipic acid (maximum 33 wt%), glutaric acid (maximum 50 wt%) and succinic acid (maximum 31 wt%) is available from BASF, Ludwigshafen, Germany under the trade mark Sokalan DCS, and a similar mixture of sodium salts under the trade mark Sokalan DCN.
• Particulate detergent compositions containing succinates as powder structurants are described and claimed in EP 61 295B (Unilever).
• compositions of the invention include fluorescers, antiredeposition agents, inorganic salts such as sodium sulphate, enzymes, lather control agents, fabric softening agents, pigments, coloured speckles, and perfumes. This list is not intended to be exhaustive.
• Detergent compositions of the invention may be prepared by any suitable method.
• the particulate detergent compositions which are the preferred embodiment of the invention are suitably prepared by spray-drying a slurry of compatible heat-insensitive ingredients, and then spraying on or postdosing those ingredients unsuitable for processing via the slurry.
• the skilled detergent formulator will have no difficulty in deciding which ingredients should be included in the slurry and which should not.
• Both the aluminosilicate and the citrate builder components are suitable for inclusion in the slurry, although it may be advantageous for processing reasons for part of the aluminosilicate to be incorporated post-tower.
• the particulate detergent compositions of the invention may be prepared to any suitable bulk density.
• Compositions having bulk densities of at least 400 g/l, more preferably at least 500 g/l, are of especial interest.
• Detergent powders containing a mixed anionic/nonionic detergent-active system, zeolite 4A, sodium citrate and a TAED/sodium perborate bleach system were prepared, by spray-drying and postdosing, in accordance with the following general formulation:
• Example 1 zeolite/citrate builder systems as follows:
• Detergencies were assessed by washing five different test cloths in a Siemens Siwamat (Trade Mark) 660 front-loading automatic washing machine in 40° French hard water (Ca:Mg ratio 7:1) at 60°C.
• test cloths used were as follows:
• Detergent powders containing a mixed anionic/nonionic detergent-active system, zeolite 4A, sodium citrate and a TAED/sodium perborate bleach system were prepared, by spray-drying and postdosing, in accordance with the following formulations:
• a detergent powder containing a mixed anionic/nonionic detergent-active system, zeolite 4A, sodium citrate and a TAED/sodium perborate bleach system and having good detergency and good powder properties was prepared, by spray-drying and postdosing, in accordance with the following formulation:
• Bleach-free detergent powders containing a higher level of zeolite 4A were prepared, by spray-drying and postdosing, in accordance with the following general formulation:
• Examples 5 and 6 and Comparative Examples E to G contained zeolite/citrate builder systems as follows:
• Detergent powders containing a mixed anionic/nonionic detergent-active system, zeolite MAP, sodium citrate and a TAED/sodium perborate bleach system were prepared to the following formulations (in parts by weight):
• Example 9 was identical to Example 7 except that the zeolite MAP was replaced by 26.00 parts of zeolite 4A.
• the zeolite MAP was prepared on a pilot scale by the method described in Examples 1 to 3 of EP 384 070A (Unilever). Its silicon to aluminium ratio was 1.10 and it had a tetragonally distorted cubic crystal structure.

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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)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)
• Silicates, Zeolites, And Molecular Sieves (AREA)

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• 1990
  • 1990-03-19 GB GB909006171A patent/GB9006171D0/en active Pending
• 1991
  • 1991-03-05 GB GB919104613A patent/GB9104613D0/en active Pending
  • 1991-03-15 EP EP19910302218 patent/EP0448298A1/de not_active Withdrawn
  • 1991-03-18 CA CA002038490A patent/CA2038490A1/en not_active Abandoned
  • 1991-03-18 CA CA002038491A patent/CA2038491C/en not_active Expired - Lifetime
  • 1991-03-19 JP JP3130756A patent/JPH04227692A/ja active Pending
  • 1991-03-19 BR BR919101075A patent/BR9101075A/pt unknown
  • 1991-03-19 ZA ZA912024A patent/ZA912024B/xx unknown
  • 1991-03-19 AU AU72969/91A patent/AU7296991A/en not_active Abandoned
  • 1991-03-19 BR BR919101074A patent/BR9101074A/pt not_active Application Discontinuation

Patent Citations (7)

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