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EP0505371A1 - Detergents liquides. - Google Patents

Detergents liquides.

Info

Publication number
EP0505371A1
EP0505371A1 EP90916476A EP90916476A EP0505371A1 EP 0505371 A1 EP0505371 A1 EP 0505371A1 EP 90916476 A EP90916476 A EP 90916476A EP 90916476 A EP90916476 A EP 90916476A EP 0505371 A1 EP0505371 A1 EP 0505371A1
Authority
EP
European Patent Office
Prior art keywords
polymers
preferred
polymer
liquid detergent
detergent composition
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.)
Granted
Application number
EP90916476A
Other languages
German (de)
English (en)
Other versions
EP0505371B1 (fr
Inventor
Stephen Graham Hales
Ezat Khoshdel
Peter Graham Montague
De Pas Johannes Cornelis Van
Adrianus Visser
Cornelis Winkel
Ronald Peter Potman
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
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0505371A1 publication Critical patent/EP0505371A1/fr
Application granted granted Critical
Publication of EP0505371B1 publication Critical patent/EP0505371B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid 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
    • 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
    • C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
    • 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
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • 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
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • 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
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/228—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with phosphorus- or sulfur-containing groups
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates

Definitions

  • the present invention relates to liquid detergent compositions, in particular to liquid detergent
  • Lamellar droplets are a particular class of surfactant structures which, inter alia, are already known from a variety of references, e.g. H.A.Barnes, 'Detergents', Ch.2. in K.Walters (Ed), 'Rheometry: Industrial
  • Such lamellar dispersions are used to endow properties such as consumer-preferred flow behaviour and/or turbid appearance. Many are also capable of suspending
  • particulate solids such as detergency builders or abrasive particles.
  • detergency builders such as kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, abrasive particles.
  • detergency builders such as abrasive particles.
  • lamellar droplets in a liquid detergent product may be detected by means known to those skilled in the art, for example optical techniques, various rheometrical measurements. X-ray or neutron diffraction, and electron microscopy.
  • the droplets consist of an onion-like configuration of concentric bi-layers of surfactant molecules, between which is trapped water or electrolyte solution (aqueous phase). Systems in which such droplets are close-packed provide a very desirable combination of physical
  • the viscosity and stability of the product depend on the volume fraction of the liquid which is occupied by the droplets. Generally speaking, when the volume fraction is around 0.6, the droplets are just touching (spacefilling). This allows reasonable stability with an acceptable viscosity (say no more than 2.5 Pas,
  • This volume fraction also endows useful solid-suspending properties.
  • compositions are sometimes less preferred for
  • a biodegradable deflocculating polymer incorporating into a lamellar detergent composition a biodegradable deflocculating polymer.
  • the present invention relates to a liquid detergent composition
  • a liquid detergent composition comprising a dispersion of
  • composition also comprising a biodegradable
  • compositions of the present invention are for instance described in our copending European patent application 89201530.6 (EP 346 995). and in our British patent applications 8924479.2, 8924478.4 and 8924477.6.
  • EP 346 995 European patent application
  • 8924479.2, 8924478.4 and 8924477.6 Of the general classes of polymers as described in these patent documents, only the use of biodegradable polymers is embraced within the scope of the present invention. It is believed to be well within the ability of the skilled person to select on the basis of general knowledge on polymer degradability combined with the teaching as provided in the above mentioned non-prepublished patent applications those deflocculating polymers that will be suitable for use in compositions of the invention.
  • polymers for use in compositions of the invention satisfy one or more of the following tests:
  • This test involves a modified SCAS test as described above, wherein the SCAS effluent is used as the inoculum in a modified Sturm test-system.
  • a 60 % conversion to CO 2 in the Sturm system using the acclimatised SCAS inoculum is an indication of inherent biodegradability.
  • any detected 14 CO 2 is a sign of biodegradability, the amount of detected 14 CO 2 is a measure of the extent of biodegradability. For example an amount of detected 14 CO 2 after 100 days corresponding to more than 20 wt % of the initial carbon-14 content of the test material is an indication of reasonable biodegradation, while more than 50 wt % would be an indication of very good
  • detected 14 CO 2 is a sign of biodegradability
  • the amount of detected 14 CO 2 is a measure of the extent of biodegradability. For example an amount of detected 14 CO 2 corresponding to more than 40 or 50 wt % of the initial carbon content of the test material would be an indication of very good biodegradation.
  • biodegradation or adsorption is estimated by measuring the removal of test material by dissolved organic carbon analysis. It is believed that a 80 % removal is a reasonable indication of biodegradability or adsorption, (h) continuous activated sludge simulation tests using radiolabelled polymers. In this test non- radiolabelled polymer is continuously dosed and
  • radiolabelled polymer is only dosed after an adaptation period of up to 2 months. During the period of
  • a preferred way of distinguishing between a non- preferred polymer and a preferred biodegradable polymer involves a combination of tests b) and c) mentioned above as follows:
  • Preferred polymer materials provide more than 80 % removal in the Modified SCAS test and more than 60 % conversion in the Sturm test-system using a SCAS inoculum.
  • Polymers which provide less than 80 % removal in the modified SCAS test are less preferred for use in compositions of the invention, while composition which provide more than 80 % removal in the SCAS test but less than 60 % conversion in the STURM test-system using a SCAS inoculum are moderately preferred for use in composition of the invention.
  • a preferred class of polymers for use in compositions of the invention are biodegradable polymers having a hydrophilic backbone and at least one hydrophobic side chain.
  • hydrophilic backbone and one or more hydrophobic side- chains is described in EP 89201530.6 (EP 346 995).
  • hydrophilic backbone of the polymer is predominantly linear (the main chain of the backbone constitutes at least 50 %, preferably more than 75 %, most preferred more than 90% by weight of the backbone), suitable monomer constituents of the hydrophilic
  • backbone are for example unsaturated C 1-6 acids, ethers, alcohols, aldehydes, ketones or esters, sugar units, alkoxy units, maleic anhydride and saturated
  • polyalcohols such as glycerol.
  • suitable monomer units are acrylic acid, alpha hydroxy acrylic acid, alpha hydroxy methyl hydroxy acid, methacrylic acid, maleic acid, vinyl acetic acid, glucosides, ethylene oxide and glycerol.
  • the hydrophilic backbone made from the backbone constituents in the absence of hydrophobic side-groups is relatively water-soluble at ambient temperature and a pH of between 6.5 and 14.0.
  • the solubility is more than 1 g/l, more preferred more than 5 g/l most preferred more than 10 g/l.
  • hydrophobic sidegroups are composed of relatively hydrophobic alkoxy groups for example
  • hydrophobic groups may be connected to the hydrophilic backbone directly or via relatively hydrophilic linkages for example a poly ethoxy linkage.
  • Preferred polymers are of the formula:
  • z is 1, q is preferably at least 1, (q+x+y) : z is from 4 : 1 to 1,000 : 1, preferably from 6 : 1 to 250 : 1; in which the monomer units may be in random order; y preferably being from 0 up to the value of x; n is at least 1; q is preferably at least 1; x may be 0.
  • R 1 represents -CO-O-, -O-, -O-CO-, -CH 2 -, -CO-NH- or is absent;
  • R 2 represents from 1 to 50 independently selected alkyleneoxy groups preferably ethylene oxide or
  • R 3 represents hydrogen or contains no more than 4 carbon atoms, then R 2 must contain an alkyleneoxy group preferably more than 5 alkyleneoxy groups with at least 3 carbon atoms; R 3 represents a phenylene linkage, or is absent;
  • R 4 represents hydrogen or a C 1-24 alkyl or C 2-24 alkenyl group, with the provison that when R 2 is absent, R 4 is not hydrogen and when also R 3 is absent, then R 4 must contain at least 5 carbon atoms;
  • R 5 represents hydrogen or a group of formula -COOA 4 ;
  • R 6 represents hydrogen or C 1-4 alkyl
  • R 12 represents -H, -CO-CH 3 , -CH 2 -COOA 4 ,
  • a 1 , A 2 , A 3 and A 4 are independently selected from hydrogen, alkali metals, alkaline earth metals, ammonium and amine bases and C 1-4 , or (C 2 H 4 O) t H wherein t is from 1-50, and wherein the monomer units may be in random order.
  • Each B 1 is independently selected from -CH 2 OH, -OH or -H;
  • a 1 -A 4 and B 1 may
  • polysaccharides independently be selected form the groups mentioned above.
  • Other preferred polymers are hydrophobically modified polysaccharides. Possible sugar units for use in those polymers include glucosides and fructosides for example maltoses, fructoses, lactoses, glucoses and galactoses. Also mixtures of sugar groups may be used. The sugar groups may be connected to each other via any suitable linkage, although 1-4 linkages and/or 1-6 linkages and/or 1-2 linkages are preferred.
  • the polysaccharides are preferably predominantly linear, but also branched polymers may be used. Especially preferred is the use of hydrophobically modified dextrans, more preferably of dextrans having a molecular weight of 2,000 to 20,000.
  • An example of a preferred polysaccharide has the
  • Each R 7 ' is R 7 or -R 1 -R 2 -R 3 -R 4 ;
  • R 7 is independantly selected from -OH, -NH-CO-CH 3 , -SO 3 A 1 , -OSO 3 A 1 , -NHSO 3 A 1 , -COOA 1 ; R 7 is preferably -OH n is the total number of -R 1 -R 2 -R 3 -R 4 groups per
  • R 1 is as defined above for formula I, or can be -NHCO-; -OCH 2 CONH-; or -O-CH 2 -CO-O-;
  • R 2-4 are as defined for formula I;
  • a 1 is as defined for formula I.
  • a second example of a preferred Hydrophobically modified polysugar is of the formula:
  • R 7 , R 7 ', R 1-4 , A 1 , v and w, m and n are as defined above. It is believed that on the basis of these formulas, the skilled person will be able to derive similar formulas for other polysaccharide polymers for use in
  • compositions of the invention are provided.
  • z and n are as defined for formula I; (x+y) : z is from 4 : 1 to 1,000 : 1, preferably from 6 : 1 to 250 : 1; y preferably being from zero up to a maximum equal to the value of x; wherein the monomer units may be in random order.
  • R 1-6 are as defined for formula I;
  • R 8 and R 9 represent -CH 2 - or are absent;
  • S 1 and S 2 are independantly selected from
  • D is -H or -OH; n is at least 1;
  • Each A 2 is A 1 or R 10 ;
  • Q 1 : Q 2 is from 4 :1 to 1,000 : 1, preferably from 6 : 1 to 250 : 1;
  • R 10 represents a C 5-24 alk(en)yl group
  • R ) 11 represents -CH 2 -, -C 2 H 4 -, -C 3 H 6 -, or an aryl link said aryl link optionally being substituted with one or more -COOA 1 groups, or a benzophenone link;
  • a 1 is as defined for formula I.
  • polymers for use in compositions have a molecular weight (determined as in our co-pending
  • Polymers according to formulas II-IV preferably have a molecular weight of 500-250,000, more preferred from 1,000-100,000, most preferably from 2,000 to 50,000.
  • Polymers according to formula I preferably are low molecular weight polymers, preferably having a molecular weight of less than 50,000, more preferred less than 10,000, especially preferred less than 5,000, most preferably from 500 to 2,000.
  • the polymers for use in detergent compositions of the invention may be prepared by using conventional polymerisation
  • condensation polymerisation suitable methods are for example described in the above mentioned co-pending European patent application.
  • the deflocculating polymer will be used at from 0.01 to 5 % by weight of the composition, more preferably from 0.1 to 3.0, especially preferred from 0.25 to 2.0 %.
  • the Applicants have hypothesised that the polymers exert their action on the composition by the following mechanism.
  • the hydrophobic side-chain(s) or ionic groups could be incorporated in or onto the outer bi-layer of the droplets, leaving the hydrophilic or nonionic backbone over the outside of the droplets and/or the polymers could be incorporated deeper inside the droplet.
  • compositions according to the invention are physically stable and have a relatively low viscosity.
  • deflocculating polymer is less stable and/or has a higher viscosity.
  • the corresponding active level sometimes advantageously the corresponding
  • composition minus the polymer is less stable and/or has a lower viscosity.
  • physical stability for these systems can be defined in terms of the maximum separation compatible with most
  • the 'stable' compositions will yield no more than 10 %, preferably no more than 5 %, most preferred no more than 2% by volume phase separation as evidenced by appearance of 2 or more separate phases when stored at 25°C for 21 days from the time of preparation.
  • compositions of the invention have a pH of between 6 and 14, more preferred from 6.5 to 13, especially preferred from 7 to 12.
  • compositions of the invention preferably have a
  • viscosity of less than 2,500 mPas at 21 s-1 more preferred less than 1,500 mPas, most preferred less than 1,000 mPas, especially preferred between 100 and 750 mPas at 21 s-1.
  • compositions of the invention also comprise detergent active materials, preferably at a level of from 1 to 70% by weight of the composition, more preferred a level of 5 to 40 % by weight, most preferred from 10 to 35 % by weight.
  • the detergent-active material in general, may comprise one or more surfactants, and may be selected from anionic, cationic, nonionic, zwitterionic and amphoteric species, and (provided mutually compatible) mixtures thereof.
  • surfactants may be selected from any of the classes, sub-classes and specific materials described in 'Surface Active Agents' Vol. I, by Schwartz & Perry, Interscience 1949 and
  • Suitable nonionic surfactants include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example
  • nonionic detergent compounds are alkyl (C 6 -C 18 ) primary or secondary linear or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine.
  • nonionic detergent compounds include long chain tertiary amine oxides, long-chain tertiary
  • the level of nonionic surfactant materials is from 1 -40 % by weight of the composition, more
  • compositions of the present invention may contain synthetic anionic surfactant ingredients, which are preferably present in combination with the above
  • surfactants are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C 8 -C 18 ) alcohols produced, for example, from tallow or coconut oil, sodium and
  • sulphonates sodium and potassium salts of sulphuric acid esters of higher (C 8 -C 18 ) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and
  • alkane monosulphonates such as those derived by reacting alpha-olefins (C 8 - 20 ) with sodium bisulphite and those derived from reacting paraffins with SO 2 and Cl 2 and then hydrolyzing with a base to produce a random
  • olefin sulphonate and olefin sulphonates, which term is used to describe the material made by reacting olefins, particularly C 10 -C 20 alpha-olefins, with SO 3 and then neutralizing and hydrolyzing the reaction product.
  • the preferred anionic detergent compounds are sodium
  • the level of the above mentioned non-soap anionic surfactant materials is from 1-40 % by weight of the composition, more preferred from 2 to 25 %. It is also possible, and sometimes preferred, to
  • an alkali metal soap of a mono- or di-carboxylic acid especially a soap of an acid having from 12 to 18 carbon atoms, for example oleic acid, ricinoleic acid, alk(en)yl succinate for example dodecyl succinate, and fatty acids derived from castor oil, rapeseed oil, groundnut oil, coconut oil, palmkernel oil or mixtures thereof.
  • the sodium or potassium soaps of these acids can be used.
  • compositions of the invention is from 1-35 % by weight of the composition, more preferred from 5-25 %.
  • compositions optionally also contain electrolyte in an amount sufficient to bring about lamellar
  • compositions contain from 1% to 60%, especially from 10 to 45% of a salting-out electrolyte.
  • Salting-out electrolyte has the meaning ascribed to in specification EP-A-79 646.
  • some salting-in electrolyte (as defined in the latter specification) may also be
  • compositions are included. In any event, it is preferred that compositions
  • detergency builder material some or all of which may be
  • detergency builders include the water-soluble salts, especially alkali metalpyrophosphates, orthophosphates, polyphosphates and phosphonates.
  • specific examples of inorganic phosphate builders include sodium and potassium
  • Phosphonate sequestrant builders may also be used. Sometimes it is however preferred to minimise the amount of phosphate builders.
  • detergency builders when present, include water-soluble alkali metal carbonates, bicarbonates, silicates and crystalline and amorphous aluminosilicates. Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and
  • potassium bicarbonates silicates and zeolites.
  • electrolytes which promote the solubility of other electrolytes, for example use of potassium salts to promote the solubility of sodium salts.
  • electrolytes which promote the solubility of other electrolytes, for example use of potassium salts to promote the solubility of sodium salts.
  • organic detergency builders when present, include the alkaline metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl carboxylates and polyhydroxysulphonates.
  • Citric acids or salts thereof are preferred builder materials for use in compositions of the invention.
  • compositions of the present invention alternatively, or in addition to the partly dissolved polymer, yet another polymer which is substantially totally soluble in the aqueous phase and has an electrolyte resistance of more than 5 grams sodium nitrilotriacetate in 100ml of a 5% by weight aqueous solution of the polymer, said second polymer also having a vapour pressure in 20% aqueous solution, equal to or less than the vapour pressure of a reference 2% by weight or greater aqueous solution of polyethylene glycol having an average molecular weight of 6000; said second polymer having a molecular weight of at least 1000.
  • Use of such polymers is generally described in our EP 301,883. Typical levels are from 0.5 to 4.5% by weight.
  • the level of non-soap builder material is from 5-40 % by weight of the composition, more preferred from 5 to 25 % by weight of the composition.
  • a number of optional ingredients may also be present, for example lather boosters such as alkanolamides,
  • monoethanolamides derived from palm kernel fatty acids and coconut fatty acids particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, lather depressants, oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors, chlorine-releasing bleaching agents such as trichloroisocyanuric acid, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes, enzymes such as proteases, amylases and Upases (including Lipolase (Trade Mark) ex Novo), enzyme stabilisers, antiredeposition agents, germicides and colourants.
  • oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate
  • peracid bleach precursors chlorine-releasing bleaching agents such as trichloroisocyanuric acid
  • inorganic salts such as sodium sulphate
  • fluorescent agents perfumes
  • enzymes such as proteases, amylases and Upases (including Lipolase
  • compositions of the invention of biodegradable
  • compositions of the invention may be prepared by any conventional method for the preparation of liquid detergent compositions.
  • a preferred method involves the dispersing of the electrolyte ingredient (if present) together with the minor ingredients except for the temperature sensitive ingredients -if any- in water of elevated temperature, followed by the addition of the builder material- if any-, the detergent active material (possibly as a premix) under stirring and thereafter cooling the mixture and adding any temperature sensitive minor ingredients such as enzymes perfumes etc.
  • the deflocculating polymer may for example be added after the electrolyte ingredient or as the final ingredient. Preferably the deflocculating polymers are added prior to the formation of the lamellar structure.
  • the detergent compositions of the invention will be diluted with wash water to form a wash liquor for instance for use in a washing machine.
  • concentration of liquid detergent composition in the wash liquor is preferably from 0.1 to 10 %, more preferred from 0.1 to 3% by weight.
  • Polymer A1 is of the basic formula I, wherein R1 is -CO-O-, R 2 and R 3 are absent, R 4 is -C 14 H 29 , R 5 is
  • R 6 is -CH 3
  • R 12 is -CO-CH 3
  • a 2 and A 3 are Na
  • x is 0, q:y is 1 : 1, (q+y):z is 25:1, Mw (cf n) is
  • Polymer C1 was of the basic structure of formula III, wherein x is zero, y is 25, R 9 is -CH 2 -, R 6 is -CH 3 , R 5 is -H, S 2 is -COCH 2 C(OH) (COOA 1 ) CH 2 COOA 1 , A 1 is Na, R is -CO-O-, R 2 and R 3 are absent, R 4 is -C 12 H 25 , Mw (cf n) is 24,000.
  • Polymer D1 was of the basic formula IV, wherein A 1 is
  • R 11 is R 10 is -C 14 H 29 , A 2 is -C 14 H 29 , Q 1 :Q 2 is 25 :1, Mw (cf n) is 2,500, D is -H
  • the SCAS effluent is used as the inoculum in a modified Sturm test-system and the following conversion
  • polymers B1 and D1 are in the preferred class of biodegradable materials because they also show more than 60 % conversion in this test. Because of its good deflocculating properties combined with the
  • polymers B1 and other polysugars are preferred embodiments of biodegradable deflocculating polymers according to the invention.
  • compositions were prepared by either adding the citrate together with sufficient NaOH to neutralise the active materials and to bring the pH of the final composition to 7, to water at a temperature of 30 °C under stirring, followed by addition of the deflocculating polymer and a premix of the Synperonic and Dobs (in acid form) (Method abbreviated WEPA) or by using the same order of addition except that the polymer is now added after the premix of the surfactants (Method abbreviated WEAP).
  • Polymers B1 to B6 are of the basic structure of formula II, wherein R 2 and R 3 are absent, R 4 is -C 14 H 29 , R 7 is -OH, R 7 ' is -OH or -R 1 -R 2 -R 3 -R 4 ;
  • compositions 28 and 29 were tested for their physical stability, both were stable (no phase separation upon storage for 21 days at 25 °C). It is believed that the viscosity reduction and the stability increase upon addition of the deflocculating polymers is an indication of deflocculating effectiveness of the polymer materials. Confirmation of this can be found in the visual appearance of the product and from
  • hydrophobically modified polysugars in combination with their excellent biodegradability renders these polymers particularly preferred for use in
  • compositions of the invention are provided.
  • Polymers A1 and A2 are of the basic structure of formula I, wherein for A1 and A2 R 1 is -CO-O-, R 2 and R 3 are absent, R 4 is -C 14 H 29 , R 5 is -COONa, R 6 is CH 3 , R 12 is -CO-CH 3 , A 1 to A 3 is Na, x is zero, q:y is 1:1, (q+y):z is 25:1.
  • the molecular weight (cf n) of A1 is 12,400, the Mw of A2 is 49,000.
  • Polymers A3 to A6 are also in accordance to formula I, wherein R 1 is -CO-O-, R 2 and R 3 are absent, R 4 is
  • R 5 is -H
  • R 6 is -CH 3
  • a 1 is Na
  • y is zero
  • q:x is 1:1
  • (q+x):z is 25:1
  • B 1 -H.
  • A3 R 12 is -CO-CH 3 and the mW (cf n) is 4,500
  • A4 R 1 2 is -H and the Mw is 2,800
  • A5 R 12 is -CO-CH 3 and the Mw is 4,300
  • A6 R 12 is -H and the Mw is 3,100.
  • Polymer A7 is in accordance with formula I, wherein R 1 is -CO-O-, R 2 and R 3 are absent, R 4 is -C 13 H 27 , R 5 is -H, R 12 is -CO-CH 3 or -CO-CH 2 -CH 2 -COONa while the ratio of -CO-CH 3 groups to -CO-CH 2 -CH 2 -COONa is 25 : 70, x and y are zero, q:z is 19:1 and the Mw (cf n) is 1,500.

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  • Detergent Compositions (AREA)

Abstract

Composition détergente liquide comprenant une dispersion de gouttelettes lamellaires en phase continue aqueuse, ainsi qu'un polymère défloculant biodégradable.
EP90916476A 1989-12-12 1990-11-14 Detergents liquides Expired - Lifetime EP0505371B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB898928067A GB8928067D0 (en) 1989-12-12 1989-12-12 Detergent compositions
GB8928067 1989-12-12
PCT/EP1990/001962 WO1991009109A1 (fr) 1989-12-12 1990-11-14 Detergents liquides

Publications (2)

Publication Number Publication Date
EP0505371A1 true EP0505371A1 (fr) 1992-09-30
EP0505371B1 EP0505371B1 (fr) 1996-03-06

Family

ID=10667830

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90916476A Expired - Lifetime EP0505371B1 (fr) 1989-12-12 1990-11-14 Detergents liquides

Country Status (6)

Country Link
EP (1) EP0505371B1 (fr)
CA (1) CA2070817A1 (fr)
DE (1) DE69025770T2 (fr)
ES (1) ES2084043T3 (fr)
GB (1) GB8928067D0 (fr)
WO (1) WO1991009109A1 (fr)

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8924478D0 (en) * 1989-10-31 1989-12-20 Unilever Plc Detergent compositions
GB2256646A (en) * 1991-06-11 1992-12-16 Unilever Plc Liquid detergent composition
SK53294A3 (en) 1993-05-07 1995-04-12 Albright & Wilson Concentrated aqueous mixture containing surface active matter and its use
US5489397A (en) * 1994-03-04 1996-02-06 National Starch And Chemical Investment Holding Corporation Aqueous lamellar detergent compositions with hydrophobically terminated hydrophilic polymer
US5599784A (en) * 1994-03-04 1997-02-04 National Starch And Chemical Investment Holding Corporation Aqueous lamellar detergent compositions with hydrophobically capped hydrophilic polymers
US5437810A (en) * 1994-04-26 1995-08-01 Colgate-Palmolive Co. Aqueous liquid detergent compositions containing oxidized polysaccharides
ZA955191B (en) * 1994-07-06 1996-12-23 Colgate Palmolive Co Aqueous liquid detergent compositions containing deflocculating polymers
EP0703243B1 (fr) * 1994-09-26 2000-12-13 Unilever N.V. Procédé pour la préparation d'une composition détergente liquide.
US5627273A (en) * 1995-01-31 1997-05-06 National Starch And Chemical Investment Holding Corporation Method for preparing hydrophobically-terminated polysaccharide polymers and detergent compositions comprising the polysaccharide polymers
EP0776965A3 (fr) 1995-11-30 1999-02-03 Unilever N.V. Compositions de polymères
NO20073834L (no) 2006-07-21 2008-01-22 Akzo Nobel Chemicals Int Bv Sulfonerte podede kopolymerer
CN102549034B (zh) 2009-07-31 2014-12-10 阿克佐诺贝尔股份有限公司 用于个人护理方面的杂化共聚物组合物
US8636918B2 (en) 2011-08-05 2014-01-28 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of controlling hard water scale
US8853144B2 (en) 2011-08-05 2014-10-07 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of improving drainage
US8679366B2 (en) 2011-08-05 2014-03-25 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of controlling hard water scale
US8841246B2 (en) 2011-08-05 2014-09-23 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage
IN2014DN03123A (fr) 2011-11-04 2015-05-22 Akzo Nobel Chemicals Int Bv
WO2013064648A1 (fr) 2011-11-04 2013-05-10 Akzo Nobel Chemicals International B.V. Copolymères dendritiques greffés, et procédés de production associés
US8945314B2 (en) 2012-07-30 2015-02-03 Ecolab Usa Inc. Biodegradable stability binding agent for a solid detergent
AU2013351426B2 (en) 2012-11-29 2015-11-26 Unilever Plc Polymer structured aqueous detergent compositions
US9365805B2 (en) 2014-05-15 2016-06-14 Ecolab Usa Inc. Bio-based pot and pan pre-soak

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3378637D1 (en) * 1982-07-27 1989-01-12 Procter & Gamble Liquid detergent compositions comprising coacervate mixture of alkylcellulose and carboxymethylcellulose and method for preparing them
US4488981A (en) * 1983-09-06 1984-12-18 A. E. Staley Manufacturing Company Lower alkyl glycosides to reduce viscosity in aqueous liquid detergents
CA1323280C (fr) * 1987-07-31 1993-10-19 Mario Bulfari Detergents liquides
GB8813978D0 (en) * 1988-06-13 1988-07-20 Unilever Plc Liquid detergents

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9109109A1 *

Also Published As

Publication number Publication date
DE69025770D1 (de) 1996-04-11
WO1991009109A1 (fr) 1991-06-27
EP0505371B1 (fr) 1996-03-06
GB8928067D0 (en) 1990-02-14
ES2084043T3 (es) 1996-05-01
DE69025770T2 (de) 1996-09-05
CA2070817A1 (fr) 1991-06-13

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