EP0774505B1 - Waschmittelzusammensetzungen - Google Patents

Waschmittelzusammensetzungen Download PDF

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Publication number
EP0774505B1
EP0774505B1 EP96306111A EP96306111A EP0774505B1 EP 0774505 B1 EP0774505 B1 EP 0774505B1 EP 96306111 A EP96306111 A EP 96306111A EP 96306111 A EP96306111 A EP 96306111A EP 0774505 B1 EP0774505 B1 EP 0774505B1
Authority
EP
European Patent Office
Prior art keywords
sodium
silicate
granular
soluble
zeolite
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.)
Revoked
Application number
EP96306111A
Other languages
English (en)
French (fr)
Other versions
EP0774505A1 (de
Inventor
Mark Phillip Houghton
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
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0774505A1 publication Critical patent/EP0774505A1/de
Application granted granted Critical
Publication of EP0774505B1 publication Critical patent/EP0774505B1/de
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

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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
    • C11D3/08—Silicates
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion 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

Definitions

  • the present invention relates to granular laundry detergent compositions of high bulk density containing zeolite builders.
  • Laundry detergent compositions containing zeolite builders have been widely disclosed in the art.
  • the present invention is based on the discovery that sodium silicate may be incorporated in high bulk density zeolite-built granular detergent compositions at an optimum level which minimises corrosion of aluminium and enamel while having no adverse effect on dissolution or solubility.
  • EP 552 054A discloses a high bulk density zeolite-built bleaching detergent powder containing 4 wt% of sodium disilicate.
  • the invention accordingly provides the use of water-soluble sodium silicate in an amount of from 2.5 to 6.5 wt% in a granular laundry detergent composition having a bulk density of at least 650 g/litre and comprising one or more detergent surfactants and a builder system comprising from 10% to 70% (anhydrous basis), preferably from 25% to 50% by weight of the total composition of zeolite, to minimise aluminium and enamel corrosion without an adverse effect on solubility.
  • Preferred granular detergent compositions to which the present invention applies comprise:
  • the separate granules of sodium silicate are in the form of granular sodium disilicate.
  • the sodium silicate is in the form of sodium carbonate/sodium silicate cogranules.
  • the amount of soluble sodium silicate in the detergent compositions with which the invention is concerned is from 2.5 to 6.5 wt%, preferably from 3 to 6 wt% and most preferably from 3 to 4 wt%. In this range corrosion of both enamel and aluminium is minimised without detriment to solubility properties.
  • detergent compositions with which the invention is concerned contain as essential ingredients detergent surfactants and detergency builders, the latter comprising zeolite (sodium aluminosilicate).
  • Surfactants and builders are preferably wholly or predominantly within a non-spray-dried base powder which may suitably constitute from 35 to 97.5 wt%, preferably from 40 to 80 wt% and most preferably from 50 to 75 wt%, of the total product.
  • Detergent surfactants are suitably present in an amount of from 5 to 60 wt% based on the whole composition.
  • the surfactants may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active compounds, and mixtures thereof.
  • Many 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 C 8 -C 15 ; primary and secondary alkylsulphates, particularly C 8 -C 15 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 C 8 -C 20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -C 15 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 alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
  • the detergent compositions also contain one or more detergency builders.
  • the total amount of detergency builder in the compositions will suitably range from 5 to 80 wt%, preferably from 10 to 60 wt%.
  • the builder system includes a crystalline sodium aluminosilicate (zeolite).
  • zeolite crystalline sodium aluminosilicates
  • Sodium aluminosilicates are incorporated in amounts of from 10 to 70% by weight (anhydrous basis), preferably from 25 to 50 wt%.
  • the alkali metal aluminosilicate has the general formula: 0.8-1.5 Na 2 O. Al 2 O 3 . 0.8-6 SiO 2
  • These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g.
  • the preferred sodium aluminosilicates contain 1.5-3.5 SiO 2 units (in the formula above). These materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
  • Suitable crystalline sodium aluminosilicate ionexchange detergency builders are described, for example, in 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.
  • the zeolite may be the commercially available zeolite 4A now widely used in laundry detergent powders.
  • the zeolite builder is maximum aluminium zeolite P (zeolite MAP) as described and claimed in EP 384 070A (Unilever).
  • 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, more preferably about 1.00.
  • the calcium binding capacity of zeolite MAP is generally at least 150 mg CaO per g of anhydrous material.
  • a supplementary builder may be present.
  • organic builders are citrates, suitably used in amounts of from 5 to 50 wt%, preferably from 10 to 35 wt%; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, preferably from 1 to 10 wt%.
  • compositions contain sodium citrate.
  • Citrate may be present in the base powder, or as separate granules, or both.
  • the detergent compositions according to the invention may also suitably contain a bleach system, preferably comprising a peroxy bleach compound, for example, an inorganic persalt or organic peroxyacid, capable of yielding hydrogen peroxide in aqueous solution.
  • a peroxy bleach compound for example, an inorganic persalt or organic peroxyacid, capable of yielding hydrogen peroxide in aqueous solution.
  • Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate is especially preferred.
  • the peroxy bleach compound is suitably present in an amount of from 5 to 35 wt%, preferably from 10 to 25 wt%.
  • the peroxy bleach compound may be used in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures.
  • the bleach precursor is suitably present in an amount of from 1 to 8 wt%, preferably from 2 to 5 wt%.
  • Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and peroxybenzoic acid precursors; and peroxycarbonic acid precursors.
  • An especially preferred bleach precursor suitable for use in the present invention is N,N,N',N'-tetracetyl ethylenediamine (TAED).
  • a bleach stabiliser may also be present.
  • Suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA) and the polyphosphonates such as Dequest (Trade Mark), EDTMP.
  • the detergent compositions may also suitably contain detergency enzymes, for example, proteases, lipases, cellulases and amylases. Enzymes are commonly employed in granular form in amounts of from about 0.1 to about 3.0 wt%.
  • the detergent compositions may contain alkali metal, preferably sodium, carbonate, in order to increase detergency and ease processing.
  • Sodium carbonate may suitably be present in amounts ranging from 1 to 60 wt%, preferably from 2 to 40 wt%.
  • compositions containing little or no sodium carbonate are also within the scope of the invention.
  • Powder flow may be improved by the incorporation in the base powder of a small amount of a powder structurant, for example, a fatty acid (or fatty acid soap), a sugar, or an acrylate or acrylate/maleate polymer.
  • a powder structurant for example, a fatty acid (or fatty acid soap), a sugar, or an acrylate or acrylate/maleate polymer.
  • a powder structurant for example, a fatty acid (or fatty acid soap), a sugar, or an acrylate or acrylate/maleate polymer.
  • fatty acid soap suitably present in an amount of from 1 to 5 wt%.
  • compositions according to the invention include soil release polymers; antiredeposition agents such as cellulosic polymers; fluorescers; inorganic salts such as sodium sulphate; lather control agents or lather boosters as appropriate; dyes; coloured speckles; perfumes; foam controllers; and fabric softening compounds.
  • Detergent compositions according to the invention may be prepared by any method suitable for the preparation of granular high bulk density compositions. Mixing and grnaulation processes using a high-speed mixer/granulator are preferably used. Suitable processes are disclosed, for example, in EP 340 013A, EP 367 339A, EP 390 251A and EP 420 317A (Unilever).
  • High bulk density granular detergent compositions were prepared to the following general formulation.
  • the base powder was prepared by mixing and granulation in a Lödige high-speed mixer/granulator, and other ingredients were postdosed as shown.
  • Base powder Coconut primary alcohol sulphate 12.00
  • Sodium soap 1.79
  • Sodium citrate 3.52
  • Sodium carbonate 2.38
  • Enamel corrosion, aluminium corrosion and insoluble residues in the wash were determined as follows.
  • Enamel corrosion was measured using the Bayer Lantern test in accordance with DIN 51154.
  • the Bayer Lantern is a closed thermostated vessel with a number of "windows" to which enamel test pieces are clamped so as to remain in contact with detergent solution with which the vessel is filled. Solutions (10 g/l) of each formulation in demineralised water were stirred in the vessel at 95°C for 24 hours. The enamel test plates were weighed before and after testing and the weight losses recorded.
  • Aluminium corrosion was measured as follows. Standard aluminium discs (composition Al >99%, Si 0.25%, Fe 0.4%, Cu 0.05%, Mn 0.05%, Mg 0.05%, Zn 0.07%) of radiums 2.5 cm were suspended in a 1-litre beaker containing a 10 g/l solution in demineralised water of each formulation for three intervals each of 7 hours. The solutions were stirred using a 6 cm magnetic stirrer bar without forming a vortex. The aluminium test plates (discs) were weighted after three 7-hour test intervals and the total weight loss recorded.
  • Standard aluminium discs composition Al >99%, Si 0.25%, Fe 0.4%, Cu 0.05%, Mn 0.05%, Mg 0.05%, Zn 0.07%
  • a washing machine test was used to determine the extent that insoluble residues were deposited on washed articles.
  • the machine used was a Siemens Siwamat (Trade Mark) 3803 front-loading automatic washer, the load was 1 kg of clean cotton, and the test methodology was as follows.
  • the machine was operated on the wool wash cycle at a wash temperature of 40°C, using water of 15° French hardness and a water inlet temperature of 20°C.
  • the sachets were removed, line dried flat, opened and turned inside out, and the level of powder residue on the inside surface of each sachet determined by visual assessment using a scoring system of 1 to 3: a score of 3 corresponds to a residue of approximately 75 wt% of the powder, while 1 indicates no residue.
  • a panel of five assessors was used to judge each sachet and allot a score. With each test product the wash process was carried out six times and the scores were averaged over the six runs.

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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)

Claims (8)

  1. Verwendung eines wasserlöslichen Natriumsilicats in einer Menge von 2.5 bis 6,5 Gew.-% in einer körnigen Waschmittelzusammensetzung, die eine Schüttdichte von mindestens 650 g/Liter hat und eine oder mehrere waschaktive Substanzen und ein Buildersystem umfaßt, das 10 bis 70 Gew.-% (wasserfreie Basis), vorzugsweise 25 bis 50 Gew.-%, der gesamten Zusammensetzung an Zeolith umfaßt, wodurch die Korrosion von Aluminium und Emaille ohne nachteiligen Einfluß auf die Löslichkeit minimiert wird.
  2. Verwendung nach Anspruch 1, wobei die körnige Waschmittelzusammensetzung umfaßt:
    (a) ein nicht durch Zerstäubungstrocknung erhaltenes Grundpulver mit einer Schüttdichte von mindestens 650 g/l, das eine oder mehrere waschaktive Substanzen und ein Buildersystem umfaßt, das einen Zeolith umfaßt, und
    (b) von 2,5 bis 6,5 Gew.-% eines löslichen Natriumsilicats in Form einzelner Körner.
  3. Verwendung nach Anspruch 2, wobei das lösliche Silicat in Form von körnigem Natriumdisilicat vorliegt.
  4. Verwendung nach Anspruch 2, wobei das lösliche Silicat in Form eines gemischten Natriumcarbonat/Natriumsilicat-Korns vorliegt.
  5. Verwendung nach einem der vorstehenden Ansprüche, wobei die körnige Waschmittelzusammensetzung 3 bis 6 Gew.-% lösliches Natriumsilicat umfaßt.
  6. Verwendung nach einem der vorstehenden Ansprüche, wobei die körnige Waschmittelzusammensetzung 3 bis 4 Gew.-% lösliches Natriumsilicat umfaßt.
  7. Verwendung nach einem der vorstehenden Ansprüche, wobei die körnige Waschmittelzusammensetzung außerdem Natriumcitrat umfaßt.
  8. Verwendung nach einem der vorstehenden Ansprüche, wobei die körnige Waschmittelzusammensetzung außerdem Natriumpercarbonat umfaßt.
EP96306111A 1995-11-17 1996-08-21 Waschmittelzusammensetzungen Revoked EP0774505B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9523571 1995-11-17
GBGB9523571.9A GB9523571D0 (en) 1995-11-17 1995-11-17 Detergent compositions

Publications (2)

Publication Number Publication Date
EP0774505A1 EP0774505A1 (de) 1997-05-21
EP0774505B1 true EP0774505B1 (de) 2001-11-21

Family

ID=10784064

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96306111A Revoked EP0774505B1 (de) 1995-11-17 1996-08-21 Waschmittelzusammensetzungen

Country Status (4)

Country Link
EP (1) EP0774505B1 (de)
DE (1) DE69617170T2 (de)
ES (1) ES2168442T3 (de)
GB (1) GB9523571D0 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9609699D0 (en) * 1996-05-09 1996-07-10 Unilever Plc Detergent compositions

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4446035A (en) * 1981-09-25 1984-05-01 The Procter & Gamble Company Cleansing agents and the like with amino-silanes
US4540443A (en) * 1984-06-15 1985-09-10 Union Carbide Corporation Cooling system cleaning composition

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5423997A (en) * 1991-05-31 1995-06-13 Colgate Palmolive Co. Spray dried powdered automatic dishwashing composition containing enzymes
ATE133637T1 (de) * 1991-07-02 1996-02-15 Crosfield Joseph & Sons Silicate
SK278834B6 (sk) * 1992-01-17 1998-03-04 Unilever Nv Časticová bieliaca detergentná zmes
AU3524093A (en) * 1992-03-27 1993-09-30 Kao Corporation Nonionic powdery detergent composition and process for producing the same
EP0639639B2 (de) * 1993-08-17 2010-07-28 The Procter & Gamble Company Percarbonat-Bleichmittel enthaltende Waschmittelzusammensetzungen
DK0677580T3 (da) * 1994-04-14 2002-11-25 Procter & Gamble Detergentsammensætning omfattende farveoverføringsinhibitorer og fremgangsmåde til fremstilling deraf
DE4419745A1 (de) * 1994-06-06 1995-12-07 Henkel Kgaa Granuliertes wasserlösliches kieselsäurehaltiges Alkalisilicat

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4446035A (en) * 1981-09-25 1984-05-01 The Procter & Gamble Company Cleansing agents and the like with amino-silanes
US4540443A (en) * 1984-06-15 1985-09-10 Union Carbide Corporation Cooling system cleaning composition

Also Published As

Publication number Publication date
DE69617170T2 (de) 2002-06-06
EP0774505A1 (de) 1997-05-21
GB9523571D0 (en) 1996-01-17
DE69617170D1 (de) 2002-01-03
ES2168442T3 (es) 2002-06-16

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