EP0505371B1 - Flüssige waschmittel - Google Patents

Flüssige waschmittel Download PDF

Info

Publication number
EP0505371B1
EP0505371B1 EP90916476A EP90916476A EP0505371B1 EP 0505371 B1 EP0505371 B1 EP 0505371B1 EP 90916476 A EP90916476 A EP 90916476A EP 90916476 A EP90916476 A EP 90916476A EP 0505371 B1 EP0505371 B1 EP 0505371B1
Authority
EP
European Patent Office
Prior art keywords
polymers
test
absent
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.)
Expired - Lifetime
Application number
EP90916476A
Other languages
English (en)
French (fr)
Other versions
EP0505371A1 (de
Inventor
Stephen Graham Hales
Ezat Khoshdel
Peter Graham Montague
Johannes Cornelis Van De Pas
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/de
Application granted granted Critical
Publication of EP0505371B1 publication Critical patent/EP0505371B1/de
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 compositions which comprise a dispersion of lamellar droplets in an aqueous continuous phase.
  • 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 Applications', J. Wiley & Sons, Letchworth 1980.
  • 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. Examples of such structured liquids without suspended solids are given in US patent 4 244 840, whilst examples where solid particles are suspended are disclosed in specifications EP-A-160 342; EP-A-38 101; EP-A-140 452 and also in the aforementioned US 4 244 840. Others are disclosed in European Patent Specification EP-A-151 884, where the lamellar droplet are called 'spherulites'.
  • 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 stability and solid-suspending properties with useful flow properties.
  • 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 (space-filling). This allows reasonable stability with an acceptable viscosity (say no more than 2.5 Pas, preferably no more than 1 Pas at a shear rate of 21s ⁇ 1). This volume fraction also endows useful solid-suspending properties.
  • a problem in formulating detergent compositions comprising polymeric ingredients, is that these compositions are sometimes less preferred for environmental reasons, because the polymeric ingredients are often less biodegradable.
  • the present invention relates to a liquid detergent composition
  • a liquid detergent composition comprising a dispersion of lamellar droplets in an aqueous continuous phase, said composition also comprising a biodegradable deflocculating polymer, selected from the four classes described below.
  • Suitable deflocculating polymer types for use in compositions of the present invention are for instance described in our copending European patent application 89201530.6 (EP 346 995) (published on 20 December 1989). and in our non-prepublished patent applications WO/91/06622 (published on 16 May 1991), WO/91/06623 (published on 16 May 1991) and GB 2,237,813 (published on 15 May 1991). 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.
  • Suitable tests for determining biodegradability are given in the OECD Guidelines. Other suitable tests involve the detection of released CO2 upon decomposition of the polymer material, in these tests sometimes 14C labelled polymers may be used. Although it is preferred that polymers for use in composition of the invention satisfy most or all of the available tests, applicants have found that polymers satisfying one or more biodegradability tests are suitable for use in the present invention.
  • Polymers for use in compositions of the invention must satisfy one or more of the following tests:
  • 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.
  • the first class of polymers for use in compositions of the invention are biodegradable polymers having a hydrophilic backbone and at least one hydrophobic side chain.
  • the basic structure of polymers having a hydrophilic backbone and one or more hydrophobic side-chains is described in EP 89201530.6 (EP 346 995).
  • the 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 C1 ⁇ 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.
  • solubility is more than 1 g/l, more preferred more than 5 g/l most preferred more than 10 g/l.
  • the hydrophobic sidegroups are composed of relatively hydrophobic alkoxy groups for example butylene oxide and/or propylene oxide and/or alkyl or alkenyl chains having from 5 to 24 carbon atoms.
  • the 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.
  • A1, A, A3 and A4 are independently selected from hydrogen, alkali metals, alkaline earth metals, ammonium and amine bases and C1 ⁇ 4, or (C2H4O) t H wherein t is from 1-50, and wherein the monomer units may be in random order.
  • Each B1 is independently selected from -CH2OH, -OH or -H;
  • A1-A4 and B1 may independently be selected from the groups mentioned above.
  • the second class of polymers for use in the present compositions are hydrophobically modified polysaccharides.
  • Possible sugar units for use in those polymers include glucosides and fructosides for example maltoses, fructoses, lactoses, glucoses and galactoses.
  • 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.
  • 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 following formula: Wherein:
  • a second example of a preferred Hydrophobically modified polysugar is of the formula: Wherein R7, R 7' , R1 ⁇ 4, A1, v and w, m and n are as defined above.
  • the third class of polymers for use in the present compositions are of the formula: Wherein:
  • the fourth class of polymers for use in the present compositions are of the formula: Wherein: D is -H or -OH; n is at least 1; Wherein:
  • polymers for use in compositions have a molecular weight (determined as in our co-pending patent application EP 346 995) of between 500 and 500,000.
  • 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 procedures, such as radical polymerisation or 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, i.e. a corresponding composition minus the deflocculating polymer is less stable and/or has a higher viscosity.
  • physical stability for these systems can be defined in terms of the maximum separation compatible with most manufacturing and retail requirements. That is, 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-l, 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 chosen from any of the classes, sub-classes and specific materials described in 'Surface Active Agents' Vol.I, by Schwartz & Perry, Interscience 1949 and 'Surface Active Agents' Vol.II by Schwartz, Perry & Berch (Interscience 1958), in the current edition of "McCutcheon's Emulsifiers & Detergents" published by the McCutcheon division of Manufacturing Confectioners Company or in 'Tensid-Taschenbuch', H.Stache, 2nd Edn., Carl Hanser Verlag, München & Wien, 1981.
  • Suitable nonionic surfactants include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide, either alone or with propylene oxide.
  • Specific nonionic detergent compounds are alkyl (C6-C18) 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.
  • Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long-chain tertiary phospine oxides and dialkyl sulphoxides.
  • the level of nonionic surfactant materials is from 1 -40 % by weight of the composition, more preferred from 2-20 %.
  • compositions of the present invention may contain synthetic anionic surfactant ingredients, which are preferably present in combination with the above mentioned nonionic materials.
  • Suitable anionic 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 (C8-C18) alcohols produced, for example, from tallow or coconut oil, sodium and potassium alkyl (C9-C20) benzene sulphonates, particularly sodium linear secondary alkyl (C10-C15) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C8-C18) 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 neutralized with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane
  • 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 %.
  • 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.
  • the level of soap in compositions of the invention is from 1-35 % by weight of the composition, more preferred from 5-25 %.
  • salting out resistant active materials such as for example described in EP 328 177, especially the use of alkyl poly glycoside surfactants such as for example disclosed in EP 70 074. Also alkyl mono glucosides may be used.
  • compositions optionally also contain electrolyte in an amount sufficient to bring about lamellar structuring of the detergent-active material.
  • compositions Preferably 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 included.
  • compositions according to the present invention include detergency builder material, some or all of which may be electrolyte.
  • detergency builder material some or all of which may be electrolyte.
  • some detergent active materials such as for example soaps, also have builder properties.
  • Examples of phosphorus containing inorganic detergency builders include the water-soluble salts, especially alkali metalpyrophosphates, orthophosphates, polyphosphates and phosphonates.
  • Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates and hexametaphosphates. Phosphonate sequestrant builders may also be used. Sometimes it is however preferred to minimise the amount of phosphate builders.
  • non-phosphorus-containing inorganic 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
  • 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. Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilitriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids, CMOS, tartrate mono succinate, tartrate di succinate and citric acid. 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 l00ml 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.
  • lather boosters such as alkanolamides, 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 lipases (including Lipolase (Trade Mark) ex Novo), enzyme stabilizers, antiredeposition agents, germicides and colorants.
  • lather boosters such as alkanolamides, 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 salt
  • 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 and R3 are absent, R4 is -C14H29, R5 is -COONa, R6 is -CH3, R1 is -CO-CH3, A and A3 are Na, x is 0, q:y is 1 : 1, (q+y):z is 25:1, Mw (cf n) is 12,400.
  • Polymer C1 was of the basic structure of formula III, wherein y is zero, x is 25, R9 is -CH2-, R6 is -CH3, R5 is -H, S is -COCH2C(OH) (COOA1)CH2COOA1, A1 is Na, R l is -CO-O-, R and R3 are absent, R4 is -C12H25, Mw (cf n) is 24,000.
  • Polymer D1 was of the basic formula IV, wherein A1 is -Na, R11 is is -C14H29, A is -C14H29.
  • Q1:Q 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 percentages were obtained:
  • polymers A1 to D1 all are within our definition of biodegradability because they provide more than 80 % removal in the modified SCAS test, while the comparative polymer as disclosed in EP 346 995 is outside our biodegradability definition by both tests.
  • the results of using the effluent of the SCAS test as the inoculum in a Sturm test-system indicate that 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 preferred improved biodegradability, polymers B1 and other polysugars (preferably of formula II or IIa) 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).
  • WEPA Synperonic and Dobs
  • Polymers B1 to B6 are of the basic structure of formula II, wherein R and R3 are absent, R4 is -C14H29, R7 is -OH, R 7' is -OH or -R1-R-R3-R4; Polymer m:n R1 Mw (cf v and w) B1 75 -O- 10,000 B2 30 -OCH2CONH 10,000 B3 75 -O- 4,000 B4 95 -O- 15,000 B5 150 -O- 35,000 B6 90 -O- 60,000
  • compositions other than the comparative formulations 1, 8 and 25 did not not yield the rapid phase separation as observed in the comparative formulations.
  • 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 microscopical observations.
  • Polymers A1 and A2 are of the basic structure of formula I, wherein for A1 and A2 R1 is -CO-O-, R and R3 are absent, R4 is -C14H29, R5 is -COONa, R6 is CH3, R1 is -CO-CH3, A1 to A3 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.
  • R1 is -CO-CH3 and the mW (cf n) is 4,500
  • A4 R 1 2 is -H and the Mw is 2,800
  • A5 R1 is -CO-CH3 and the Mw is 4,300
  • A6 R1 is -H and the Mw is 3,100.
  • Polymer A7 is in accordance with formula I, wherein R1 is -CO-O-, R and R3 are absent, R4 is -C13H27, R5 is -H, R1 is -CO-CH3 or -CO-CH2-CH2-COONa while the ratio of -CO-CH3 groups to -CO-CH2-CH2-COONa is 25 : 70, x and y are zero, q:z is 19:1 and the Mw (cf n) is 1,500.

Claims (8)

  1. Flüssiges Waschmittel, umfassend eine Dispersion von lamellaren Tröpfchen eines Waschmittelaktivstoffs in einer wässerigen kontinuierlichen Phase, wobei das Mittel ebenfalls ein Entflockungspolymer umfaßt, ausgewählt aus der Gruppe, bestehend aus:
    (I) Polymeren mit einem hydrophilen Gerüst und einer oder mehreren hydrophoben Seitenketten;
    (II) hydrophob modifizierten Polysacchariden;
    (III) Polymeren der Formel:
    Figure imgb0015
     worin z 1 ist und n mindestens 1 ist; (x+y) : z 4 : 1 bis 1000 : 1 ist, worin die Monomereinheiten in zufälliger Reihenfolge vorliegen können;
    R¹ -CO-O-, -O-, -O-CO-, -CH₂-, -CO-NH- wiedergibt oder nicht vorliegt;
    R 1 bis 50 unabhängig voneinander ausgewählte Alkylenoxygruppen wiedergibt oder nicht vorliegt, mit der Maßgabe, daß wenn R³ nicht vorliegt, R⁴ Wasserstoff wiedergibt oder nicht mehr als 4 Kohlenstoffatome enthält, R dann eine Alkylenoxygruppe, vorzugsweise mehr als 5 Alkylenoxygruppen mit mindestens 3 Kohlenstoffatomen, enthalten muß;
    R³ eine Phenylenbindung wiedergibt oder nicht vorliegt;
    R⁴ Wasserstoff oder eine C₁₋₂₄-Alkyl- oder C₂₋₂₄-Alkenylgruppe wiedergibt, mit der Maßgabe daß, wenn R nicht vorliegt, R⁴ nicht Wasserstoff ist, und wenn ebenfalls R³ nicht vorliegt, R⁴ dann mindestens 5 Kohlenstoffatome enthalten muß;
    R⁵ Wasserstoff oder eine Gruppe der Formel -COOA⁴ wiedergibt;
    R⁶ Wasserstoff oder C₁₋₄-Alkyl wiedergibt;
    R⁸ und R⁹ -CH₂- wiedergeben oder nicht vorliegen;
    S¹ und S unabhängig voneinander ausgewählt sind aus -CO(CH₂)₂COOA¹, -CO(CH)₂COOA¹, -COCH₂C(OH) (COOA¹)CH₂COOA¹, -COCH₂COOA¹, -CO(CH(OH))₂COOA¹, -COCH₂CH(OH)COOA¹, -COCH₂CH(CH₃)COOA¹ und -COCH₂C(=CH₂)COOA¹;
    A1 unabhängig ausgewählt ist aus Wasserstoff, Alkalimetallen, Erdalkalimetallen, Ammonium- und Aminbasen und C₁₋₄ oder (C₂H₄O)tH, worin t 1-50 ist und worin die Monomereinheiten in zufälliger Reihenfolge sein können; und (IV) Polymere der Formel
    Figure imgb0016
     worin: D -H oder -OH darstellt und n mindestens 1 ist;
    Figure imgb0017
     ist
    worin:
    A jeweils A¹ oder R¹⁰ darstellt;
    Q¹ : Q 4 : 1 bis 1000 : 1 ist;
    R¹⁰ eine C₅₋₂₄-Alk(en)ylgruppe wiedergibt;
    B -O-CO-R¹¹-CO- darstellt;
    R¹¹ -CH₂-, -C₂H₄-, -C₃H₆- oder eine Arylbindung wiedergibt, wobei die Arylbindung gegebenenfalls substituiert ist mit einer oder mehreren -COOA¹-Gruppen oder einer Benzophenonbindung;
    A¹ unabhängig ausgewählt ist aus Wasserstoff, Alkalimetallen, Erdalkalimetallen, Ammonium- und Aminbasen und C₁₋₄ oder (C₂H₄O)tH, worin t 1-50 ist und worin die Monomereinheiten in zufälliger Reihenfolge sein können;
    das Polymer einem oder mehreren der nachstehenden Bioabbaubarkeitstests genügt:
    (a) Modifizierter Sturm-Test;
    (b) Modifizierter SCAS-Test;
    (c) Kombinierter modifizierter SCAS-Test und Sturm-Test;
    (d) Chargenweiser Belebtschlammtest von ¹⁴C-markierten Polymeren (e) Schmutzbioabbaubarkeitstest von ¹⁴CO₂-markierten Polymeren;
    (f) Anaerober Batch-Test von ¹⁴C-markierten Polymeren;
    (g) Kontinuierliche Belebtschlamm-Simulationstests; und
    (h) Kontinuierlicher Belebtschlamm-Simulationstest unter Verwendung von radiomarkierten Polymeren.
  2. Flüssigwaschmittel nach Anspruch 1, wobei das Entflockungspolymer ein hydrophob modifizierter Polyzucker ist.
  3. Flüssigwaschmittel nach Anspruch 2, wobei der Polyzucker ein hydrophob modifiziertes Dextran, vorzugsweise mit einem Molekulargewicht von 2000 bis 20000 ist.
  4. Flüssigwaschmittel nach Anspruch 1 mit einer Viskosität von weniger als 2500 mPas bei 21 s⁻¹.
  5. Flüssigwaschmittel nach Anspruch 1, umfassend 0,01 - 5 Gewichtsprozent Entflockungspolymere.
  6. Flüssigwaschmittel nach Anspruch 1 mit einem pH-Wert von 6 bis 14.
  7. Flüssigwaschmittel nach Anspruch 1, umfassend 1-70 Gewichtsprozent Waschmittelaktivstoffe.
  8. Flüssigwaschmittel nach Anspruch 1, das weniger als 10 Volumenprozent Phasentrennung ergibt, wenn es bei 25°C für 21 Tage ab dem Tag der Herstellung gelagert wird.
EP90916476A 1989-12-12 1990-11-14 Flüssige waschmittel Expired - Lifetime EP0505371B1 (de)

Applications Claiming Priority (3)

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

Publications (2)

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

Family

ID=10667830

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90916476A Expired - Lifetime EP0505371B1 (de) 1989-12-12 1990-11-14 Flüssige waschmittel

Country Status (6)

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

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US8674021B2 (en) 2006-07-21 2014-03-18 Akzo Nobel N.V. Sulfonated graft copolymers
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
US8853144B2 (en) 2011-08-05 2014-10-07 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of improving drainage
US8945314B2 (en) 2012-07-30 2015-02-03 Ecolab Usa Inc. Biodegradable stability binding agent for a solid detergent
US9051406B2 (en) 2011-11-04 2015-06-09 Akzo Nobel Chemicals International B.V. Graft dendrite copolymers, and methods for producing the same
US9109068B2 (en) 2005-07-21 2015-08-18 Akzo Nobel N.V. Hybrid copolymer compositions
US9365805B2 (en) 2014-05-15 2016-06-14 Ecolab Usa Inc. Bio-based pot and pan pre-soak
US9988526B2 (en) 2011-11-04 2018-06-05 Akzo Nobel Chemicals International B.V. Hybrid dendrite copolymers, compositions thereof and methods for producing the same

Families Citing this family (11)

* 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 (de) * 1994-09-26 2000-12-13 Unilever N.V. Verfahren zur Herstellung einer flüssigen Detergenszusammensetzung
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 (de) 1995-11-30 1999-02-03 Unilever N.V. Polymerzusammetzungen
BR112015012062B1 (pt) 2012-11-29 2021-07-20 Unilever Ip Holdings B.V. Composição líquida detergente aquosa estruturada com polímero

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 (en) * 1987-07-31 1993-10-19 Mario Bulfari Liquid detergent compositions
GB8813978D0 (en) * 1988-06-13 1988-07-20 Unilever Plc Liquid detergents

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9109068B2 (en) 2005-07-21 2015-08-18 Akzo Nobel N.V. Hybrid copolymer compositions
US9321873B2 (en) 2005-07-21 2016-04-26 Akzo Nobel N.V. Hybrid copolymer compositions for personal care applications
US8674021B2 (en) 2006-07-21 2014-03-18 Akzo Nobel N.V. Sulfonated graft copolymers
US8841246B2 (en) 2011-08-05 2014-09-23 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage
US8853144B2 (en) 2011-08-05 2014-10-07 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of improving drainage
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
US9309489B2 (en) 2011-08-05 2016-04-12 Ecolab Usa Inc Cleaning composition containing a polysaccharide hybrid 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
US9051406B2 (en) 2011-11-04 2015-06-09 Akzo Nobel Chemicals International B.V. Graft dendrite copolymers, and methods for producing the same
US9988526B2 (en) 2011-11-04 2018-06-05 Akzo Nobel Chemicals International B.V. Hybrid dendrite copolymers, compositions thereof and methods for producing the same
US8945314B2 (en) 2012-07-30 2015-02-03 Ecolab Usa Inc. Biodegradable stability binding agent for a solid detergent
US9365805B2 (en) 2014-05-15 2016-06-14 Ecolab Usa Inc. Bio-based pot and pan pre-soak
US10053652B2 (en) 2014-05-15 2018-08-21 Ecolab Usa Inc. Bio-based pot and pan pre-soak

Also Published As

Publication number Publication date
GB8928067D0 (en) 1990-02-14
CA2070817A1 (en) 1991-06-13
DE69025770D1 (de) 1996-04-11
WO1991009109A1 (en) 1991-06-27
ES2084043T3 (es) 1996-05-01
EP0505371A1 (de) 1992-09-30
DE69025770T2 (de) 1996-09-05

Similar Documents

Publication Publication Date Title
EP0505371B1 (de) Flüssige waschmittel
AU641954B2 (en) Liquid detergents
US5750489A (en) Liquid detergent compostions containing structuring polymers for enhanced suspending power and good pourability
EP0346995A2 (de) Flüssige Reinigungsmittel
EP0499623B1 (de) Waschmittelzusammensetzungen
GB2237813A (en) Liquid detergent
EP0502860A1 (de) Flüssige waschmittel
AU651797B2 (en) Liquid detergents
EP0498806B1 (de) Waschmittelzusammensetzungen
AU652543B2 (en) Liquid detergents
EP0504155B1 (de) Flüssiges waschmittel
AU667660B2 (en) Liquid detergents
GB2256646A (en) Liquid detergent composition
EP0652935B1 (de) Waschmittelzusammensetzung

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19920603

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): CH DE ES FR GB GR IT LI NL SE

RBV Designated contracting states (corrected)

Designated state(s): CH DE ES FR GB IT LI NL SE

17Q First examination report despatched

Effective date: 19950620

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UNILEVER N.V.

Owner name: UNILEVER PLC

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE ES FR GB IT LI NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19960306

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: E. BLUM & CO. PATENTANWAELTE

REF Corresponds to:

Ref document number: 69025770

Country of ref document: DE

Date of ref document: 19960411

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2084043

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
ITF It: translation for a ep patent filed

Owner name: JACOBACCI & PERANI S.P.A.

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19961030

Year of fee payment: 7

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19971130

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19971130

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20001016

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20011115

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

EUG Se: european patent has lapsed

Ref document number: 90916476.6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20021017

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20021106

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20021202

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20021204

Year of fee payment: 13

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20031114

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20031115

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040602

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20031114

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040730

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20031115

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20051114