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EP0448297A1 - Compositions détergentes - Google Patents

Compositions détergentes Download PDF

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Publication number
EP0448297A1
EP0448297A1 EP19910302217 EP91302217A EP0448297A1 EP 0448297 A1 EP0448297 A1 EP 0448297A1 EP 19910302217 EP19910302217 EP 19910302217 EP 91302217 A EP91302217 A EP 91302217A EP 0448297 A1 EP0448297 A1 EP 0448297A1
Authority
EP
European Patent Office
Prior art keywords
detergent composition
zeolite map
composition
zeolite
detergent
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP19910302217
Other languages
German (de)
English (en)
Inventor
Jelles Vincent Boskamp
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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
Priority claimed from GB909006171A external-priority patent/GB9006171D0/en
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0448297A1 publication Critical patent/EP0448297A1/fr
Withdrawn legal-status Critical Current

Links

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, containing a detergency builder system which is a combination of a specific aluminosilicate and a citrate builder salt.
  • 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.
  • EP 384 070A (Unilever) describes and claims a novel zeolite P (maximum aluminium zeolite P, or zeolite MAP) having an especially low silicon to aluminium ratio, not greater than 1.33 and preferably not greater than 1.15. This material is demonstrated to be a more efficient detergency builder than conventional zeolite 4A.
  • the present invention is based on the discovery that the novel combination of zeolite MAP and citrate provides an especially effective detergency builder system.
  • EP 419 036A (Unilever), to be published on 27 March 1991, describes and claims a detergency builder additive for use in a Baukasten (building block) product in conjunction with a separately packaged main wash detergent powder, the additive comprising:
  • the present invention provides a detergent composition for fabric washing, comprising:
  • the present invention provides a detergency builder composition comprising:
  • the invention 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 above and/or a detergency builder composition as defined above.
  • the invention provides the use of citric acid and/or a salt thereof as a detergency builder in a detergency builder composition or a detergent composition for fabric washing containing zeolite MAP.
  • the detergent composition is a mixture of the detergent composition
  • 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 of the invention contains two essential components: zeolite MAP and a citrate.
  • Zeolite MAP and its use in detergent compositions are described and claimed in EP 384 070A (Unilever). It is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range of from 0.9 to 1.33, and more preferably within the range of from 0.9 to 1.2.
  • zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and having a tetragonally distorted cubic crystal structure.
  • zeolite MAP having a silicon to aluminium ratio not greater than 1.07.
  • Zeolite MAP generally has a calcium binding capacity of at least 150 mg CaO per g of anhydrous aluminosilicate.
  • zeolite MAP like other zeolites contains water of hydration, for the purposes of the present invention amounts and percentages of zeolite are expressed in terms of the anhydrous material.
  • the second essential component of the detergency builder system 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 weight ratio of aluminosilicate to citrate is preferably within the range of from 1:1 to 6:1, more preferably from 1.5:1 to 3:1.
  • Detergent compositions of the invention preferably comprise from 10 to 45 wt%, more preferably from 12 to 30 wt%, of zeolite MAP; and from 2 to 20 wt%, more preferably from 3 to 9 wt% and most preferably from 5 to 8 wt%, of the citrate.
  • 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.
  • a bleach system preferably comprises one or more peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, which may be employed in conjunction with bleach precursors to improve bleaching action at low temperatures.
  • the bleach system preferably comprises a peroxy bleach compound, preferably an inorganic persalt, optionally in conjunction with a precursor.
  • Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate.
  • Preferred bleach precursors are peracetic acid precursors, especially tetraacetylethylene diamine (TAED); peroxybenzoic acid precursors; 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
  • 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 zeolite MAP and the citrate builder component are suitable for inclusion in the slurry, although it may be advantageous for processing reasons for part of the zeolite MAP 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.
  • the detergency builder system of the invention may be exist as a composition in its own right that may be used for water softening or added to the wash liquor to enhance the performance of an unbuilt or underbuilt detergent composition in hard water.
  • Such a composition may, for example, form the building or water-softening component of a Baukasten (building block) detergent composition as described and claimed in EP 419 036A (Unilever), to be published on 27 March 1991, in which a main wash powder is supplied together with separately packaged additives (builder, bleach) that need only be used when the wash conditions demand them.
  • Baukasten building block
  • additives builder, bleach
  • a typical composition of this type might contain from 50 to 80 wt% zeolite MAP (anhydrous basis), and from 5 to 30 wt% sodium citrate.
  • a composition of this type may in principle contain no components other than the two essential components (zeolite MAP and citrate), although in practice it may be desirable to include other ingredients, for example, sodium carbonate, and binders such as nonionic surfactants or cellulose derivatives.
  • zeolite MAP and citrate zeolitic MAP and citrate
  • binders such as nonionic surfactants or cellulose derivatives.
  • builder additives of the specific composition claimed in EP 419 036A are disclaimed and do not form part of the present invention.
  • a builder composition of the type under discussion may also be used as a raw material or premix in the manufacture of more fully formulated detergent compositions.
  • the invention also includes within its scope detergent compositions prepared by admixing the two builder materials (zeolite MAP and citrate) separately and independently with other detergent ingredients.
  • Detergent powders containing zeolite MAP and citrate were prepared to the following formulations (in parts by weight):
  • Comparative Example A was identical to Example 1 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.
  • Formulations containing lower percentages of zeolite MAP and citrate were prepared as follows:
  • the zeolite MAP used was the same as that used in Examples 1 and 2.
  • Sokalan (Trade Mark) CP5 ex BASF AG, Ludwigshafen, Germany is an acrylic/maleic copolymer.

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
EP19910302217 1990-03-19 1991-03-15 Compositions détergentes Withdrawn EP0448297A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB909006171A GB9006171D0 (en) 1990-03-19 1990-03-19 Detergent compositions
GB9006171 1990-04-19
GB9104613 1991-03-05
GB919104613A GB9104613D0 (en) 1990-03-19 1991-03-05 Detergent compositions

Publications (1)

Publication Number Publication Date
EP0448297A1 true EP0448297A1 (fr) 1991-09-25

Family

ID=26296808

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19910302217 Withdrawn EP0448297A1 (fr) 1990-03-19 1991-03-15 Compositions détergentes

Country Status (2)

Country Link
EP (1) EP0448297A1 (fr)
AU (1) AU637879B2 (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0521635A1 (fr) * 1991-06-25 1993-01-07 Unilever Plc Composition détergente ou composition sous forme particulaire
EP0502675A3 (en) * 1991-03-05 1993-01-07 Unilever Plc Detergent compositions
EP0522726A1 (fr) * 1991-06-25 1993-01-13 Unilever Plc Compositions détergentes
EP0552053A1 (fr) * 1992-01-17 1993-07-21 Unilever Plc Compositions détergentes
EP0552054A1 (fr) * 1992-01-17 1993-07-21 Unilever Plc Compositions détergentes
WO1994013773A1 (fr) * 1992-12-08 1994-06-23 Unilever Plc Compositions detergentes
WO1994028109A1 (fr) * 1993-05-26 1994-12-08 Unilever Plc Compositions detergentes
WO1994028098A1 (fr) * 1993-05-26 1994-12-08 Unilever Plc Compositions detergentes
WO1995004804A1 (fr) * 1993-08-06 1995-02-16 La Marina Patent Holding S.A. Detergent sans phosphate ni chlore
WO1995014767A1 (fr) * 1993-11-24 1995-06-01 Unilever Plc Compositions detergentes
US5447651A (en) * 1992-09-08 1995-09-05 Lever Brothers Company, Division Of Conopco, Inc. Process for producing concentrated laundry detergent by manufacture of low moisture content detergent slurries utilizing liquid active surfactant blend technology
US5453215A (en) * 1992-09-08 1995-09-26 Lever Brothers Company, Division Of Conopco, Inc. Process for producing concentrated laundry detergent by manufacture of low moisture content detergent slurries
GB2287949A (en) * 1994-03-31 1995-10-04 Procter & Gamble Laundry detergent composition
US6465417B1 (en) * 1999-07-09 2002-10-15 Colgate-Palmolive Co. Fabric cleaning composition containing zeolite
US6475982B1 (en) * 1999-11-24 2002-11-05 Colgate Palmolive Company Fabric cleaning composition containing zeolite

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9216386D0 (en) * 1992-07-31 1992-09-16 Unilever Plc Use of aluminosilicates of the zeolite p type as low temperature calcium binders

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3112176A (en) * 1961-10-04 1963-11-26 Minerals & Chem Philipp Corp Base-exchange zeolite and method for making the same
DE3144297A1 (de) * 1981-11-07 1983-05-19 Degussa Ag, 6000 Frankfurt Phosphatsubstitut fuer waschmittel
EP0313144A2 (fr) * 1987-10-23 1989-04-26 Unilever N.V. Compositions détergentes et de blanchiment sans phosphates
EP0384070A2 (fr) * 1988-11-03 1990-08-29 Unilever Plc Zéolite P, son procédé de préparation et son utilisation dans les compositions détergentes
EP0419036A2 (fr) * 1989-08-21 1991-03-27 Unilever Plc Additif renforçateur pour détergents et système le contenant

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU6491990A (en) * 1989-10-24 1991-05-02 Mervyn Rowland Ayres Building panels
GB9006171D0 (en) * 1990-03-19 1990-05-16 Unilever Plc Detergent compositions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3112176A (en) * 1961-10-04 1963-11-26 Minerals & Chem Philipp Corp Base-exchange zeolite and method for making the same
DE3144297A1 (de) * 1981-11-07 1983-05-19 Degussa Ag, 6000 Frankfurt Phosphatsubstitut fuer waschmittel
EP0313144A2 (fr) * 1987-10-23 1989-04-26 Unilever N.V. Compositions détergentes et de blanchiment sans phosphates
EP0384070A2 (fr) * 1988-11-03 1990-08-29 Unilever Plc Zéolite P, son procédé de préparation et son utilisation dans les compositions détergentes
EP0419036A2 (fr) * 1989-08-21 1991-03-27 Unilever Plc Additif renforçateur pour détergents et système le contenant

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0502675A3 (en) * 1991-03-05 1993-01-07 Unilever Plc Detergent compositions
US5238594A (en) * 1991-06-25 1993-08-24 Lever Brothers Co., Division Of Conopco, Inc. Detergent compositions
EP0522726A1 (fr) * 1991-06-25 1993-01-13 Unilever Plc Compositions détergentes
US5518649A (en) * 1991-06-25 1996-05-21 Lever Brothers Company, Division Of Conopco, Inc. Particulate detergent composition or component comprising zeolite MAP ASA carrier
EP0521635A1 (fr) * 1991-06-25 1993-01-07 Unilever Plc Composition détergente ou composition sous forme particulaire
EP0552054A1 (fr) * 1992-01-17 1993-07-21 Unilever Plc Compositions détergentes
US5259981A (en) * 1992-01-17 1993-11-09 Lever Brothers Company Detergent compositions
US5259982A (en) * 1992-01-17 1993-11-09 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions
CN1045311C (zh) * 1992-01-17 1999-09-29 尤尼利弗公司 洗涤剂组合物
CN1045310C (zh) * 1992-01-17 1999-09-29 尤尼利弗公司 洗涤剂组合物
EP0552053A1 (fr) * 1992-01-17 1993-07-21 Unilever Plc Compositions détergentes
US5447651A (en) * 1992-09-08 1995-09-05 Lever Brothers Company, Division Of Conopco, Inc. Process for producing concentrated laundry detergent by manufacture of low moisture content detergent slurries utilizing liquid active surfactant blend technology
US5453215A (en) * 1992-09-08 1995-09-26 Lever Brothers Company, Division Of Conopco, Inc. Process for producing concentrated laundry detergent by manufacture of low moisture content detergent slurries
WO1994013773A1 (fr) * 1992-12-08 1994-06-23 Unilever Plc Compositions detergentes
US5498342A (en) * 1992-12-08 1996-03-12 Lever Brothers Company Detergent composition containing zeolite map and organic peroxyacid
WO1994028109A1 (fr) * 1993-05-26 1994-12-08 Unilever Plc Compositions detergentes
WO1994028098A1 (fr) * 1993-05-26 1994-12-08 Unilever Plc Compositions detergentes
WO1995004804A1 (fr) * 1993-08-06 1995-02-16 La Marina Patent Holding S.A. Detergent sans phosphate ni chlore
WO1995014767A1 (fr) * 1993-11-24 1995-06-01 Unilever Plc Compositions detergentes
AU698980B2 (en) * 1993-11-24 1998-11-12 Unilever Plc Detergent compositions
GB2287949A (en) * 1994-03-31 1995-10-04 Procter & Gamble Laundry detergent composition
US6465417B1 (en) * 1999-07-09 2002-10-15 Colgate-Palmolive Co. Fabric cleaning composition containing zeolite
US6465418B1 (en) * 1999-07-09 2002-10-15 Colgate-Palmolive Co. Fabric cleaning composition containing zeolite
US6475982B1 (en) * 1999-11-24 2002-11-05 Colgate Palmolive Company Fabric cleaning composition containing zeolite

Also Published As

Publication number Publication date
AU7296891A (en) 1993-06-10
AU637879B2 (en) 1993-06-10

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