EP0353075A2 - Compositions détergentes liquides - Google Patents

Compositions détergentes liquides Download PDF

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Publication number
EP0353075A2
EP0353075A2 EP19890307668 EP89307668A EP0353075A2 EP 0353075 A2 EP0353075 A2 EP 0353075A2 EP 19890307668 EP19890307668 EP 19890307668 EP 89307668 A EP89307668 A EP 89307668A EP 0353075 A2 EP0353075 A2 EP 0353075A2
Authority
EP
European Patent Office
Prior art keywords
silica
detergent composition
composition according
weight
viscosity
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Withdrawn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
EP19890307668
Other languages
German (de)
English (en)
Other versions
EP0353075A3 (fr
Inventor
Derek Aldcroft
John Robert Newton
John Mark Saunders
Peter William Stanier
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
Original Assignee
Unilever PLC
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
Application filed by Unilever PLC filed Critical Unilever PLC
Publication of EP0353075A2 publication Critical patent/EP0353075A2/fr
Publication of EP0353075A3 publication Critical patent/EP0353075A3/fr
Withdrawn legal-status Critical Current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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0013—Liquid compositions with insoluble particles in suspension
    • 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

Definitions

  • the present invention relates to physically stable liquid detergent compositions and in particular to aqueous liquid detergent compositions having non-corrosive properties and satisfactory viscosities.
  • Aqueous liquid detergent compositions particularly those containing sodium tripolyphosphate corrode the enamel and aluminium parts in washing machines, and this effect is exacerbated by the presence of perborate or percarbonate salts. It is desirable to include an anti-corrosion agent in the detergent composition to inhibit the corrosive action so as to prevent the formation of corrosion products that could discolour the fabric in the wash and to prolong the useful life of the aluminium and enamel parts in the washing machine.
  • EP 0110472 discloses that the corrosive action of aqueous liquid detergent compositions can be reduced to a significant extent by incorporation of silica, usually from 1% to 10% w/w, of such type and in such amount that in the wash liquor a certain threshold concentration of dissolved silica is established. It was found that in order to achieve optimal corrosion protection the silica must be present in the wash liquor in a dissolved form at a concentration of at least 120 ppm by weight and preferably at least 150 ppm by weight.
  • Liquid detergent compositions desirably have viscosities which are not excessive so that they may be efficiently handled and dosed into washing machines.
  • the applicants have found the detergent compositions described in EP 0110472 using commercially available silicas with a BET surface area below 550m2/g ⁇ 1 have relatively high viscosities and compositions having reduced viscosity, i.e. at the level accepted as commercially desirable preferably up to about 1000 mPas, are formed by using amorphous silicas having specific physical characteristics. Viscosities above the level quoted give rise to difficulties in handling and dosing.
  • the amorphous silicas used in the present invention have a BET surface area in the range from about 200 to about 550 m2/g, a mean pore diameter from about 1.5, preferably 3, to about 11 nm, an oil absorption from about 40, preferably from about 70, to about 140 cc/100g and a weight mean particle size from about 1, preferably from about 5, to about 30 microns, preferably to about 20 microns.
  • these silicas are incorporated at a level from about 1% to about 5% w/w.
  • amorphous silicas provide the desired corrosion inhibition even at relatively low concentrations of about 2% to about 4 % w/w and at these concentrations an acceptable viscosity increase in the formulation is obtained.
  • the silica added increases the viscosity of the base composition by not more than 50% preferably not more than 40% at a level of 5% w/w.
  • Suitable forms of amorphous silica are precipitated silicas and silica gels, such as hydrogels and xerogels. Precipitated silicas are preferred.
  • the precipitated amorphous silicas used in the present invention do not give a defined pore volume to nitrogen.
  • the porosity present can only be defined by oil absorption and/or mercury intrusion volume within a stated range of pore diameters. In general mercury porosimetry is useful from about 3.0 to about 1000 nm.
  • silicas of the invention and comparison silicas it is necessary for the pore volume to be measured by the nitrogen B.E.T. Method described in Brunauer et al J. Am. Chem. SOC. Vol 60 p309 (1938). This method depends on the condensation of nitrogen into pores of silica and it is useful for measuring pores with diameters up to about 60 nm.
  • the liquid detergent compositions of the invention further comprise as essential ingredient an active detergent material, which may be an alkali metal or alkanolamine soap of C10-C24 fatty acid, including polymerized fatty acids, or an anionic, nonionic, cationic, zwitterionic or amphoteric synthetic detergent material, or a mixture of any of these.
  • active detergent material which may be an alkali metal or alkanolamine soap of C10-C24 fatty acid, including polymerized fatty acids, or an anionic, nonionic, cationic, zwitterionic or amphoteric synthetic detergent material, or a mixture of any of these.
  • the anionic synthetic detergents are synthetic detergents of the sulphate- and sulphonate-types.
  • salts including sodium, potassium, ammonium and substituted ammonium salts, such as mono-, di- and tri-ethanolamine salts
  • C9-C20 alkyl benzene sulphonates C8-C22 primary or secondary alkane sulphonates
  • C8-C24 olefin sulphonates C8-C24 olefin sulphonates
  • sulphonated polycarboxylic acids prepared by sulphonation of the pyrolized product of alkaline earth metal citrates, eg. as described in British Patent Specification No.
  • nonionic synthetic detergents are the condensation products of ethylene oxide, propylene oxide and/or butylene oxide with C8-C18 alkylphenols, C8-C18 primary or secondary aliphatic alcohols, C8-C18 fatty acid amides; further examples of nonionics include tertiary amine oxides with one C8-C18 alkyl chain and two C1-C3 alkyl chains. The above reference also describes further examples of nonionics.
  • the average number of moles of ethylene oxide and/or propylene oxide present in the above nonionics varies from 1 to 30; mixtures of various nonionics, including mixtures of nonionics with a higher degree of alkoxylation, may also be used.
  • cationic detergents are the quaternary ammonium compounds such as alkyl dimethyl ammonium halogenides.
  • amphoteric or zwitterionic detergents are N-alkylamino acids, sulphobetaines and condensation products of fatty acids with protein hydrolysates, but owing to their relatively high cost they are usually used in combination with an anionic or a nonionic detergent. Mixtures of the various types of active detergents may also be used, and preference is given to mixtures of an anionic and a nonionic detergent-active compound. Soaps (in the form of their sodium, potassium, and substituted ammonium salts) such as of polymerized fatty acids, may also be used, preferably in conjunction with an anionic and/or a nonionic synthetic detergent.
  • the amount of the active detergent material varies from about 1 to about 60%, preferably from 2 to 40% and particularly preferably from 5 to 30% by weight. When a soap is incorporated, the amount thereof is from 1 to 40% by weight.
  • the liquid compositions of the invention preferably also comprise up to 60% of suitable builder materials, such as sodium, potassium and ammonium or substituted ammonium pyro- and tri- polyphosphates, -ethylenediamine tetraacetates, -nitrilotriacetates, -ether polycarboxylates, -citrates, -carbonates, -orthophosphates, zeolites, carboxy-methyloxysuccinates.
  • suitable builder materials such as sodium, potassium and ammonium or substituted ammonium pyro- and tri- polyphosphates, -ethylenediamine tetraacetates, -nitrilotriacetates, -ether polycarboxylates, -citrates, -carbonates, -orthophosphates, zeolites, carboxy-methyloxysuccinates.
  • Particularly preferred are the polyphosphate builder salts, nitrilotriacetates, citrates,
  • the amount of water present in the detergent compositions of the invention varies from 10 to 70% by weight.
  • liquid detergent compositions of the invention for example sequestering agents, such as ethylenediamine-tetraphosphonic acid and phosphonates such as those sold under the Dequest Trade Name of Monsanto; non-builder electrolytes, such as alkalimetal-chlorides, -bromides, -nitrates and -sulphates; soil-suspending agents, such as sodium carboxymethylcellulose, polyvinylpyrrolidone or the maleic anhydride/vinylmethylether copolymer; hydrotropes; dyes; perfumes; alkaline materials, such as silicates; optical brighteners; germicides; anti-tarnishing agents; suds boosters, suds depressants, such as liquid polysiloxane anti-foam compounds; enzymes, particularly proteolytic enzymes, such as the commercially available subtilisins Maxatase (ex Gist-Brocades N.V., Delft, The Netherlands), Alcalase, Espe
  • sequestering agents such
  • liquid detergent composition was added to distilled water at 90°C at a concentration of 10 grams/litre, unless stated otherwise, and mixed using a 2.54 cm castellated stirrer for 5 minutes at 3000 rpm.
  • test method employed is described in ISO 4533 in which the standard test solution is replaced with the aqueous liquid detergent composition at a concentration of 10g/l, and the apparatus utilised in ISO 4535.
  • the oil absorption is determined by the ASTM spatula rub-out method (American Society of Test Material Standards D, 281).
  • the test is based upon the principle of mixing linseed oil with a silica by rubbing with a spatula on a smooth surface until a stiff putty-like paste is formed which will not break or separate when it is cut with the spatula.
  • the volume of oil used is then put into the following equation:-
  • the weight mean particle size of the silicas was determined with the aid of a Malvern Particlesizer, Model 3600 E. This instrument, made by Malvern Instruments, Malvern, Worcestershire uses the principle of Fraunhöffer diffraction utilising a low power He/Ne laser. Before measurement the sample was dispersed ultrasonically in water for a period of 7 minutes to form an aqueous suspension.
  • This parameter is related to the surface area and pore volume and, using a cylindrical pore model, is calculated for a silica product with the formula
  • Pore volume is measured using mercury intrusion method (viii) or nitrogen adsorption (iii).
  • Mercury intrusion volumes are determined (in cc/g) by standard mercury intrusion procedures using a Micromeritics Autopore 9220 mercury porosimeter.
  • the pore radius is calculated from the Washburn equation using values of surface tension for mercury of 485 dynes/cm and contact angle of 140°.
  • the sample Prior to measurement the sample was outgassed at room temperature to a pressure of 50 microns of mercury. The mercury intrusion volume recorded is that occurring over the range of calculated pore diameters of 0.05 to 1.0 micron.
  • Tables I and II quote silica product and test characteristics.
  • the silicas are indicated by letters which correspond to the following products.
  • silicas labelled A, B, C, D, E, F, H & M are silicas used in the invention
  • Silica M was prepared using the Example 2 test 10 conditions of GB 2038303 followed by fast drying and air micronisation.
  • Formulation A contains all the ingredients listed except for the silica, and the water balance is adjusted to allow the silicas to be added as a 20% w/w aqueous slurry in the final act of preparing the detergent composition for test.
  • formulation B the silica is added as an ingredient at the preferred place in the formulation usually before the addition of the non-ionic surfactant and the water balance adjusted accordingly.
  • detergent composition A is to screen silicas and absolute determination of product characteristics are usually only performed when the silica is incorporated into the detergent composition at the preferred place of addition, i.e. using composition B.
  • the silicas as listed in Table I were dispersed at 2% w/w loading into detergent composition A as aqueous slurries at ambient temperature using a castellated stirrer (diameter 2.54 cm) at approximately 1000 r.p.m. for 2 minutes.
  • the viscosity and corrosion inhibition of each test formulation was determined using the test methods described above.
  • Silicas A and H were dispersed at loadings of 2% to 5% w/w into detergent composition A as 20% w/w aqueous slurries at ambient temperature using the same dispersing conditions as in Example I.
  • the viscosity was determined on each test/formulation according to the method described above. Silicas H and I could not be loaded to a concentration of 5% w/w and 4% w/w respectively, owing to excessive viscosities in the aqueous slurry.
  • Silica A was dispersed into detergent composition B, prior to adding the non-ionic surfactant, at a loading of 2% w/w. Before addition, the silica was dispersed in water at a concentration of 20% w/w. Three preparations of the detergent composition containing the silica used in the invention were prepared, together with three compositions where the silica was omitted and the water balance adjusted accordingly. The viscosity of each preparation was determined according to the method described above. The results are summarised in Table IV. The data shows that the viscosity of the detergent composition does vary with each preparation, but for the formulations containing the silica used in the invention the viscosity increase is not greater than 25% in each case.
  • silicas used in the invention are capable of inhibiting the corrosive action of the detergent composition without causing undesirable increases in viscosity of the formulation.
  • these desirable features need to remain in the detergent composition for a period of at least three months.
  • Silicas A and F together with comparison silica G were dispersed at a loading of 2% w/w into detergent composition B during its preparation and before the non-ionic surfactant was added.
  • the silicas were dispersed in water at a concentration of 20% w/w before adding to the composition.
  • the viscosity and corrosion inhibition was determined for each formulation using the methods described above, and then the detergent compositions were allowed to stand for three months at ambient temperature. The tests for viscosity and corrosion inhibition were then repeated.

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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)
  • Chemical Or Physical Treatment Of Fibers (AREA)
EP89307668A 1988-07-29 1989-07-27 Compositions détergentes liquides Withdrawn EP0353075A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8818144 1988-07-29
GB888818144A GB8818144D0 (en) 1988-07-29 1988-07-29 Liquid detergent compositions

Publications (2)

Publication Number Publication Date
EP0353075A2 true EP0353075A2 (fr) 1990-01-31
EP0353075A3 EP0353075A3 (fr) 1990-04-25

Family

ID=10641349

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89307668A Withdrawn EP0353075A3 (fr) 1988-07-29 1989-07-27 Compositions détergentes liquides

Country Status (6)

Country Link
EP (1) EP0353075A3 (fr)
JP (1) JPH02255897A (fr)
AU (1) AU3906889A (fr)
BR (1) BR8903791A (fr)
GB (1) GB8818144D0 (fr)
ZA (1) ZA895779B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0482275A1 (fr) * 1990-10-22 1992-04-29 The Procter & Gamble Company Détergents liquides stables contenant un agent de blanchiment
WO2000011949A1 (fr) * 1998-08-28 2000-03-09 Crosfield Limited Porteur particulaire pour formulations biocides

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1531432A (en) * 1975-02-14 1978-11-08 Procter & Gamble Ltd Detergent compositions
US4561993A (en) * 1982-08-16 1985-12-31 The Clorox Company Thixotropic acid-abrasive cleaner
EP0110472B1 (fr) * 1982-11-26 1988-06-22 Unilever N.V. Compositions détergentes liquides
ZA887068B (en) * 1987-09-29 1990-05-30 Colgate Palmolive Co Thixotropic aqueous liquid automatic dishwashing detergent composition

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0482275A1 (fr) * 1990-10-22 1992-04-29 The Procter & Gamble Company Détergents liquides stables contenant un agent de blanchiment
TR25342A (tr) * 1990-10-22 1993-03-01 Procter & Gamble Agartici ihtiva eden kararli sivi deterjan bilesimleri
US5445756A (en) * 1990-10-22 1995-08-29 The Procter & Gamble Company Stable liquid detergent compositions containing peroxygen bleach suspended by a hydropholic silica
WO2000011949A1 (fr) * 1998-08-28 2000-03-09 Crosfield Limited Porteur particulaire pour formulations biocides
US6905698B1 (en) 1998-08-28 2005-06-14 Ineos Silicas Limited Particulate carrier for biocide formulations

Also Published As

Publication number Publication date
AU3906889A (en) 1990-02-01
JPH02255897A (ja) 1990-10-16
EP0353075A3 (fr) 1990-04-25
GB8818144D0 (en) 1988-09-01
ZA895779B (en) 1991-03-27
BR8903791A (pt) 1990-03-20

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