EP0652935B1 - Composition detergente - Google Patents

Composition detergente Download PDF

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Publication number
EP0652935B1
EP0652935B1 EP93915938A EP93915938A EP0652935B1 EP 0652935 B1 EP0652935 B1 EP 0652935B1 EP 93915938 A EP93915938 A EP 93915938A EP 93915938 A EP93915938 A EP 93915938A EP 0652935 B1 EP0652935 B1 EP 0652935B1
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absent
polymer
formula
ratio
monomer units
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EP0652935A1 (fr
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Ezat Unilever Res. Port Sunlight Khoshdel
Johannes Cornelis Unlilever Research Van De Pas
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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    • 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
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines 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
    • C11D3/37—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

Definitions

  • the present invention relates to deflocculating polymers and liquid detergent compositions comprising such polymers, in particular to liquid detergent compositions that comprise a dispersion of lamellar droplets in an aqueous continuous phase.
  • EP 346 995 describes deflocculating polymers having a hydrophilic backbone and one or more hydrophobic side-chains
  • WO 91/06622 describes deflocculating polymers being a block copolymer consisting of alternating hydrophobic and hydrophilic groups
  • WO 91/06623 describes deflocculating polymers consisting of nonionic monomers and ionic monomers
  • GB 2 237 813 describes deflocculating polymers consisting of a hydrophobic backbone and one or more hydrophilic side-chains.
  • Deflocculating polymers have been used in liquid detergents, in particular in liquid detergent compositions that comprise a dispersion of lamellar droplets in an aqueous continuous phase, as for example described in EP 346 995, WO/91/06622, WO/91/06623 and GB 2 237 813.
  • Other applications for deflocculating polymers in general purpose cleaners, liquid abrasive cleaners, liquid bleach compositions are disclosed in WO/91/09108, in fabric softening compositions in EP 415698 and the use in granular detergent compositions is disclosed in WO/91/09932.
  • WO/91/09109 discloses liquid detergent compositions comprising deflocculating polymers that are biodegradable.
  • hydrophilic backbone of the polymer is predominantly linear; the main chain or the backbone constitutes at least 50%, preferably more than 75%, most preferred more than 90% by weight of the polymer.
  • Monomer units suitable for incorporation in the hydrophilic backbone are for example unsaturated C 1-6 acids, ethers, alcohols, aldehydes 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 acrylic acid, methacrylic acid, maleic acid, vinyl acetic acid, itaconic acid, polyethoxy groups preferably comprising from 4 to 50 ethylene oxide groups, polyglycerol, condensation polymers of polyglycerol and citric acid anhydride and condensation polymers of alpha-hydroxy acids or polyacetals.
  • Each of the above monomers can be present in the hydrophilic backbone in random order, in block arrangement or in mixtures thereof.
  • 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.
  • the hydrophobic side chains are part of a monomer unit which is incorporated in the polymer by copolymerising hydrophobic monomers and the hydrophilic monomers making up the backbone of the polymer.
  • the hydrophobic side chains for this use preferably include those which when isolated from their linkage are relatively water insoluble, i.e. preferably less than 1 g/l, more preferred less than 0.5 g/l, most preferred less than 0.1 g/l of the hydrophobic monomers, will dissolve in water at ambient temperature and a pH of 3.0 to 12.5.
  • relatively hydrophobic groups are butylene oxide and/or propylene oxide and/or alkyl or alkenyl chains.
  • the hydrophobic groups may be connected to the hydrophilic backbone directly or via relatively hydrophilic linkages for example a polyethoxy linkage.
  • Deflocculating polymer being a block copolymer having alternating hydrophobic and hydrophilic groups
  • polymers have one of the following general structures: wherein A represents a hydrophobic group, B a hydrophilic group and z is an integer which is preferably zero.
  • the hydrophilic groups of the polymer are preferably composed of hydrophilic monomer units, which can be selected from a variety of units available for the preparation of polymers. Suitable hydrophilic monomer units are for instance described in the paragraph on deflocculating polymer with hydrophilic backbone and one or more hydrophobic side-chains. Particularly preferred hydrophilic groups are polyethoxy groups preferably comprising from 4 to 50 ethylene oxide groups, polyglycerol, condensation polymers of polyglycerol and citric acid anhydride and condensation polymers of alpha-hydroxy acids or polyacetals.
  • the hydrophobic groups of the polymer are preferably selected from saturated and unsaturated alkyl chains, e.g. having from 5 to 24 carbon atoms, preferably from 6 to 18, most preferred from 8 to 16 carbon atoms, and are optionally bonded to the adjacent hydrophilic groups via an alkoxylene or polyoxyalkylene linkage, for example a polypropoxy or butyloxy linkage having from 1 to 50 alkoxylene groups.
  • Other suitable hydrophobic groups are polyoxyalkylene groups comprising from 4 to 50 propylene oxide and/or butylene oxide groups.
  • hydrophilic groups may be linked to the hydrophobic groups by any possible chemical link, although the following types of linkages are preferred: -C-O-, -CO-O- or -O-.
  • the ionic-nonionic deflocculating polymer comprises a monomer A which is independently selected from the group of monomer units which are nonionic under the conditions in the liquid detergent product and a monomer B which is ionic under the conditions of the product.
  • nonionic monomer A units for use in compositions of the invention are monomers which are nonionic of character under most circumstances and monomer units which are anionic or cationic of character, but which are at the conditions such as pH of the product neutralised such that they have an appreciable nonionic character.
  • the pH of the product differs at least one unit, more preferred at least two units with the pK a value corresponding to the neutralisation of the monomer unit in the polymer.
  • Suitable monomer units which are nonionic per se are for example ethylenically unsaturated amides such as acrylamide, methacrylamide and fumaride and their N-substitued derivatives such as N-(dimethyl amino ethyl)acrylamide, vinyl alcohol, vinyl acetate, vinyl heterocyclic amides such as vinyl pyrrolidone, acrolein, allyl alcohol, hydroxy ethyl (meth) acrylate, hydroxy propyl (meth)acrylate, sugar units such as saccharides and glucosides, glycerol or other polyalcohols.
  • ethylenically unsaturated amides such as acrylamide, methacrylamide and fumaride and their N-substitued derivatives such as N-(dimethyl amino ethyl)acrylamide, vinyl alcohol, vinyl acetate, vinyl heterocyclic amides such as vinyl pyrrolidone, acrolein, ally
  • Suitable monomer units which are anionic at certain conditions, but which have an appreciable nonionic character at relatively low pH values of the product are for example: ethylenically unsaturated carboxylic acids, dicarboxylic acids such as acrylic acid, maleic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, aconitic acid and citraconic acid.
  • Suitable monomer units which are cationic under certain conditions, but which have an appreciable nonionic character at relatively high pH values are for example: amino alkyl esters of unsaturated carboxylic acids such as 2-amino ethyl (metha)crylate, dimethyl amino ethyl (meth)acrylate, diethyl amino ethyl (meth)acrylate, dimethyl amino methyl (meth) acrylate, diethyl amino ethyl (meth)acrylate, vinyl or alkyl amines such as vinyl pyridine, vinyl morpholine or allylamine.
  • amino alkyl esters of unsaturated carboxylic acids such as 2-amino ethyl (metha)crylate, dimethyl amino ethyl (meth)acrylate, diethyl amino ethyl (meth)acrylate, dimethyl amino methyl (meth) acrylate, diethyl amino ethyl (meth)acrylate, vinyl or
  • mixtures of nonionic monomers may be used.
  • the ionic monomer B may be ionic under most circumstances, but also possible is the use of monomer units which only become ionised under the pH conditions of the product. If such ionisable monomer units are used, then preferably the pH of the product should differ at least one unit, more preferred at least two units with the pK a corresponding to the ionisation of the monomer in the polymer.
  • Examples of generally ionised monomer units are N(trimethylammoniumethyl) acrylamide chloride or sulphate, N(trimethyl ammonium propyl) acrylamide chloride or sulphate, 2-suphato ethyl (meth)acrylate and its ammonium, alkali metal or alkali earth metal salts, or can be obtained by conversion reactions of monomers A such as the cationisation of sugar units with 2,3 epoxypropyl trimethyl ammonium chloride, other ethylenically unsaturated quaternary ammonium compounds such as vinyl benzyl trimethyl ammonium chloride, the quaternary ammonium salts of di methyl/ethyl amino methyl/ethyl (meth)acrylate, vinyl aryl sulphonates such as vinyl benzyl sulphonate, sodium vinyl sulphonate, sodium alkyl sulphonate, beta-styrene phosphonic acid, sodium-p styrene
  • Examples of monomer units which have an appreciable ionised character at relativly high pH values are ethylenically unsaturated carboxylic acids, dicarboxylic acids such as acrylic acid, maleic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, aconitic acid and citralinic acid.
  • Suitable monomer units which which have an appreciable ionised character at relatively low pH values are for example: amino alkyl esters of unsaturated carboxylic acids such as 2-amino ethyl (metha)crylate, dimethyl amino ethyl (meth)acrylate, diethyl amino ethyl (meth)acrylate, dimethyl amino methyl (meth) acrylate, diethyl amino ethyl (meth)acrylate, vinyl or alkyl amines such as vinyl pyridine, vinyl morpholine or allylamine.
  • amino alkyl esters of unsaturated carboxylic acids such as 2-amino ethyl (metha)crylate, dimethyl amino ethyl (meth)acrylate, diethyl amino ethyl (meth)acrylate, dimethyl amino methyl (meth) acrylate, diethyl amino ethyl (meth)acrylate, vinyl or alkyl amines such as
  • mixtures of monomer units may be used.
  • the monomers for use in ionic-nonionic polymers are sufficiently hydrophilic to form at least a 1 % by weight solution when dissolved in water of ambient temperature and of the pH of the final product.
  • ionic-nonionic polymers contain at least two different monomers.
  • the first of these monomers is preferably of nonionic character as defined hereinabove, the second monomer is preferably ionic under most circumstances as defined hereinabove.
  • the ionic monomer is a cationic monomer.
  • the amount of ionic monomers in the polymer is from 0.1 to 50 % by weight of the polymer, more preferred from 1 to 25%, most preferred from 4 to 15%.
  • a first group of preferred deflocculating polymers according to the present invention having hydrophilic backbone and one or more hydrophobic side-chains, has the formula (I): wherein:
  • 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 independently be selected from the groups mentioned above.
  • a second group of preferred deflocculating polymers of the present invention having hydrophilic backbone and one or more hydrophobic side-chains, is of the formula (II): wherein: Q 2 is a molecular entity of formula (IIa): wherein:
  • a 1 -A 4 and B 1 may independently be selected from the groups mentioned above.
  • Q 1 is a multifunctional monomer, allowing the branching of the polymer, wherein the monomers of the polymer may be connected to Q 1 in any direction, in any order, therewith possibly resulting in a branched polymer.
  • Q 1 is trimethyl propane triacrylate (TMPTA), methylene bisacrylamide or divinyl glycol.
  • a third group of preferred deflocculating polymers of the present invention having hydrophilic backbone and one or more hydrophobic side-chains, and being especially suitable for fabric softening compositions comprising an aqueous base and one or more fabric-softening materials, is of the formula (III): wherein Q 3 is derived from a monomeric unit IIIa comprising: Q 4 is derived from the molecular entity IIIb: and Q 5 is derived from a monomeric unit IIIc: wherein:
  • a fourth group of preferred deflocculating polymers of the present invention having hydrophilic backbone and one or more hydrophobic side-chains and being especially suitable for fabric softening compositions comprising an aqueous base and one or more fabric-softening materials, is of the formula (IV): wherein:
  • a fifth group of preferred deflocculating polymers of the present invention, having nonionic monomers and ionic monomers, is of the formula (V): wherein:
  • a sixth group of preferred deflocculating polymers of the present invention being a block copolymer having alternating hydrophobic and hydrophilic groups is represented by the formulae (VI): wherein:
  • the general formulae I-VI are to be construed as including those mixed copolymer forms wherein, within a particular polymer molcule where n is 2 or greater, R 1 -R 15 differ beetween individual monomer units therein.
  • Polymers for use in compositions may have a molecular weight between 500 and 1,000,000.
  • the molecular weight is measured by GPC using polyethyleneglycol standards.
  • the molecular weight of the standards are measured by the absolute intrinsic viscosity method described by Noda, Tsoge and Nagasawa in Journal of Physical Chemistry, Volume 74, (1970), page 710-719.
  • Polymers according to the invention preferably have molecular weights of from 750-100,000, more preferably of from 1,000 to 30,000, most preferably of from 2,000 to 10,000.
  • the polymers for use in detergent compositions of the invention may be prepared by using conventional polymerization procedures, such as radical polymerization, cationic-anionic polymerization or a combination thereof.
  • the ketone-group can be incorporated in the deflocculating polymer as described in our co-pending application GB 9207795.7 filed on 9 April 1992.
  • the ketone groups can for example be derived from a compound of the formula (X): wherein each of R4 and R5, which may be the same or different, represents a group capable of stabilising a free radical.
  • one of R4 and R5 represents an aryl or cyano group, and the other represents an aryl, alkyl or cyano group.
  • at least one of R4 and R5 is a phenyl group, and the compound in which R4 and R5 both represent phenyl groups is especially preferred.
  • This compound is 2,2-diphenyl-4-methylene-1,3-dioxolane.
  • Suitable tests for determining biodegradability are given in the OECD Guidelines. Other suitable tests involve the detection of released CO 2 upon decomposition of the polymer material, in these tests sometimes 14 C labelled polymers may be used.
  • polymers for use in compositions of the invention satisfy one or more of the following tests:
  • polymers for use in composition of the invention satisfy both tests, applicants have found that polymers satisfying one biodegradability tests is suitable for use in the present invention.
  • Deflocculating polymers according to the invention can for example be used in liquid detergent composisitons, general purpose cleaners, liquid abrasive cleaners, liquid bleach compositions as disclosed in WO/91/09108 and also in granular detergent compositions as disclosed in WO/91/09932.
  • Deflocculating polymers can in particular be used in liquid detergent compositions that 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 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 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 liquid 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).
  • 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.
  • Liquid 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.
  • liquid compositions of the invention comprising polymers according to formulae I, II, 2V and VI have a pH of between 6 and 14, more preferred from 6.5 to 13, especially preferred from 7 to 12.
  • liquid compositions of the invention comprising polymers according to formulae III and IV have a pH of less than 6.0, more preferred less than 5.0, especially from 1.5 to 4.5, most preferred from 2.0 to 4.0.
  • Liquid compositions of the invention comprising polymers according to formulae I and II may also have low pH, i.e. more preferred less than 5.0, especially from 1.5 to 4.5, most preferred from 2.0 to 4.0.
  • the amount of the deflocculating polymer to be used is dependent on the product form in which it is used, as well as on the function in the product. In general the deflocculating polymer will be used at levels of 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 %.
  • 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 (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.
  • Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long-chain tertiary phosphine oxides and dialkyl sulphoxides.
  • the level of nonionic surfactant materials is from 1 to 40 % by weight of the composition, more preferred from 2 to 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 (C 8 -C 18 ) alcohols produced, for example, from tallow or coconut oil, sodium and potassium alkyl (C 9 -C 20 ) benzene sulphonates, particularly sodium linear secondary alkyl (C 10 -C 15 ) benzene sulphonates; sodium alkyl glycerol 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 (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 neutralized with sodium hydroxide; sodium and potassium salts of fatty acid amides of
  • 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 include 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 phosphorous 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, nitrilotriacetic 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 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.
  • 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, anti-redeposition 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
  • Liquid 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.
  • the water and isopropanol (IPA) was charged into a reaction vessel mounted in a heating bath thermostated at 100°C and degassed with oxygen free nitrogen.
  • the DMD was dissolved in the acrylic acid-lauryl methacrylate by warming.
  • the mixed monomer solution was then added dropwise over 3 hours to the stirred water/IPA solution.
  • the persulphate initiator solution was fed in from another dropping funnel over a 4 hour period. After the addition was completed, the heating and stirring was continued for another 18 hours. This gave a sticky solid and an emulsion. 92 % of the theoretical amount of sodium hydroxide (in 30ml water) was added to achieve neutrality (pH 7).
  • the IPA was removed by distillation using a rotary evaporator and the concentrate poured into acetone to precipitate the polymer and remove benzophenone.
  • the polymer was separated, dissolved in water and precipitated again into acetone and the process repeated. Finally, the polymer was redissolved in water, filtered through glass fibre to remove the last traces of benzophenone then freeze-dried. Polymer yield 29.4g (94.5%).
  • compositions were prepared by 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).
  • Basic composition 1 Ingredients % (wt) Na Dobs 24.5 Synperonic A7 9.9 Na-citrate 2aq 16.4 Water 49.2 Deflocculation polymer weights additional to basic formulation
  • the molecular weight is 32,200.
  • the polymer is also believe to have an acceptable biodegradability.

Abstract

Polymère défloculant possédant un squelette hydrophile et une ou plusieurs chaînes latérales hydrophobes, étant un copolymère bloc ayant des groupes hydrophobes et hydrophiles alternés, ou bien ayant des monomères non ioniques et des monomères ioniques, comprenant des unités monomères renfermant un groupe cétone. Ces polymères défloculants peuvent par exemple s'utiliser dans des détergents granulaires et liquides, de préférence dans une composition détergente liquide comportant une dispersion de gouttelettes lamellaires d'une substance active détergente dans une phase continue aqueuse.

Claims (8)

  1. Polymère défloculant ayant un squelette, dans lequel le polymère a un squelette hydrophile et une ou plusieurs chaînes latérales hydrophobes, ou est un copolymère bloc ayant une alternance de groupes hydrophobes et hydrophiles, ou a des monomères non ioniques et des monomères ioniques, caractérisé en ce que le polymère défloculant comprend de 1 à 30 moles % d'unités monomères de la formule :
    Figure imgb0035
     dans le squelette.
  2. Un polymère défloculant selon la revendication 1, caractérisé en ce que le polymère a la formule I :
    Figure imgb0036
     dans laquelle :
    les unités monomères peuvent être dans un ordre aléatoire ;
    z est 1
    k est au moins 1
    n est au moins 1 (et peut être déterminé par la masse moléculaire) ;
    le rapport de (k + x + y) : Z va de 4 pour 1 à 1,000 pour 1 ;
    le rapport k : (x + y + z) va de 1 pour 99 à 30 pour 70;
    R1 représente -CO-O-, -O-, -O-CO-, -CH2-, -CO-NH- ou est absent ;
    R2 représente de 1 à 50 groupes alkylènoxy sélectionnés de façon indépendante, ou est absent, à condition que R3 soit absent et que R4 représente l'hydrogène ou ne contienne pas plus de 4 atomes de carbone, et dans ce cas R2 contient au moins 1 groupe alkylènoxy;
    R3 représente une liaison phénylène ou est absent ;
    R4 représente de l'hydrogène ou un groupe alkyle en C1-24 ou un groupe alkényle en C2-24, à condition que lorsque R2 est absent, alors R4 n'est pas de l'hydrogène, et à condition que lorsque R3 est également absent, alors R4 contient au moins 2 atomes de carbone;
    R5 représente de l'hydrogène ou un groupe de formule -COOA4 ;
    R6 représente de l'hydrogène ou un alkyle en C1-4 ; et
    A1, A2, A3 et A4 sont indépendamment sélectionnés à partir de l'hydrogène, des métaux alcalins, des métaux alcalino-terreux, des bases ammonium et amines, des C1-4, ou (C2H4O)tH dans lequel t va de 1 à 50 et dans lesquels les unités monomères peuvent être dans un ordre aléatoire.
    Chaque B1 est indépendamment sélectionné à partir de -CH2OH-, -OH ou -H ;
    Pour chaque unité monomère, R1-R6, A1-A4 et B1 peuvent être indépendamment sélectionnés à partir des groupes mentionnés ci dessus.
    formule (II) :
    Figure imgb0037
     dans laquelle Q2 est une entité moléculaire de formule (IIa) :
    Figure imgb0038
     dans laquelle :
    les unités monomères peuvent être en ordre aléatoire ;
    z et v sont 1 ;
    n est au moins 1 (et peut être déterminé à partir de la masse moléculaire) ;
    k est au moins 1 ;
    au moins une des unités monomères p, q ou r est présente ;
    le rapport de (k + x + y + p + q + r) : z va de 4 pour 1 à 1.000 pour 1;
    le rapport de k : (x + y + p + q + r + z) va de 1 pour 99 à 30 pour 70 ;
    R1 - R6, A1 - A4 et B1 sont tels que définis dans la formule I.
    R7 et R8 représentent -CH3 ou -H ;
    R9 et R10 représentent des groupes de substitution tels que des groupes aminos, amines, amides, sulphonates, sulfates, phosphonates, phosphates, hydroxy, carboxyles et oxydes ; ils sont de préférence sélectionnés à partir de -SO3Na, -CO- O-C2H4-OS3Na, -CO-O-NH-C(CH3)2-SO3Na, -CO-NH2, -O-CO-CH3, -OH ;
    Pour chaque unité monomère, R1 - R12, A1 - A4 et B1 peuvent être sélectionnés indépendant parmi les groupes mentionnés ci dessus.
    Q1 est un monomère multifonctionnel permettant la ramification du polymère, dans laquelle les monomères ou le polymère peuvent être reliés à Q1 dans n'importe quelle direction, dans n'importe quel ordre, ce qui peut avoir pour résultat un polymère ramifié.
    Formule (III) :
    Figure imgb0039
     dans laquelle Q3 est dérivé d'une unité monomère IIIa comprenant :
    Figure imgb0040
     Q4 est dérivé de l'entité moléculaire IIIb :
    Figure imgb0041
     et Q5 est dérivé de l'unité monomère IIIc :
    Figure imgb0042
     dans laquelle :
    n est au moins 1 ;
    k est au moins 1 ;
    w va de 0 à 4 ;
    le rapport de (a + b + c + k) : d va de 5 pour 1 à 500 pour 1 ;
    dans laquelle les unités monomères peuvent être en ordre aléatoire, a, b, c, d, e, f, g, h peuvent être des nombres entiers ou zéro ;
    le rapport de k : (a + b + c + d) va de 1 pour 99 à 30 pour 70 ;
    R1 - R6 sont définis tel que dans la formule I ;
    R11 et R11* sont indépendamment sélectionnés à partir de l'hydrogène ou de l'alkyle en C1 - C4 ;
    R12 est indépendamment sélectionné parmi les alkyles en C5 à C24, les alkényles, les aryl cycloalkyles, les hydroxyalkyles ou les hydroxyalkyles ; et
    B1, B2, B3 et B4 sont des anions organiques ou inorganiques ; des exemples des anions représentés par B1, B2, B3 et B4 sont les ions halides, le sulfate, le sulphonate, le phosphate, l'hydroxyde, le cyanide, le carbonate, le bicarbonate, le thiocyanate, le sulphide, le cyanate, l'acétate et les autres ions communs inorganiques et organiques.
    Formule (IV) :
    Figure imgb0043
     dans laquelle :
    z est 1 ;
    n est au moins 1 ;
    k est au moins 1
    le rapport de (j + k) : z va de 5 pour 1 à 500 pour 1 ;
    le rapport de k : (j + z) va de 1 pour 99 à 30 pour 70 ; dans laquelle les unités monomère peuvent être en ordre aléatoire ;
    R1- R6 sont tels que définis dans la formule I ;
    R13 représente -CH2-, - C2H4-, -C3H6 ou est absent ;
    R14 représente de 1 à 50 groupes alkylèneoxy sélectionnés de façon indépendante, de préférence des groupes d'oxyde d'éthylène, ou il est absent ;
    R15 représente -H ou -OH.
    Formule (V) :
    Figure imgb0044
     dans laquelle :
    les unités monomères peuvent être en ordre aléatoire ;
    z est 1
    k est au moins 1 ;
    n est au moins 1 (et peut être déterminé à partir de la masse moléculaire) ;
    le rapport de (k + x) : z va de 1 pour 1 à 2.000 pour 1 ;
    le rapport de k : (x + y) va de 1 pour 99 à 30 pour 70 ;
    R1 représente -C3H6 - N+ -(CH3)3(Cl-), -C2H4 - OSO3 - (Na+), -SO3 - (Na+), -C2H4N+ (CH3)3 Cl-, -C2H4N+ (C2H6)2 Cl-, -CH2 N+ (CH3)3 Cl-, -CH2N+ (C2H6)2 Cl- ou benzyl- SO3 - (Na+) ;
    R2 représente -CO-O-, -O-, -O-CO-, -CH2-, -CO-NH-, ou est absent ;
    R3 et R4 représentent de l'hydrogène ou un alkyle en C1-4 ;
    Ra est CH2, C2H4, C3H6 ou est absent,
    Rb représente de 1 à 50 de 1 à 50 groupes d'oxyde d'alkylène sélectionnés de façon indépendante, de préférence des groupes d'oxyde d'éthylène, ou est absent ;
    Rc représente -OH ou -H ;
    et dans laquelle si R2, Ra et Rb sont absents alors Rc n'est pas -H ;
    ou
    Formule (VI) :
    Figure imgb0045
     dans laquelle :
    les unités monomères peuvent être en ordre aléatoire ;
    x va de 4 pour 1.000 ;
    k est au moins 1 ;
    le rapport de k sur x va de 1 pour 99 à 30 pour 70 ;
    R1 représente un groupe alk(én)yle en C2-24 et/ou de 4 à 50 groupes d'oxyde de propylène ou d'oxyde de butylène;
    R2 représente -CO- ;
    R3 représente -CO-O- ou -O-.
  3. Une composition détergente liquide comprenant une dispersion de gouttelettes lamellaires de matériau détergent actif dans une phase aqueuse continue et comprenant en outre un polymère défloculant selon la revendication 1.
  4. Une composition détergente liquide selon la revendication 3, caractérisée en ce que la quantité de polymère défloculant va de 0,01 à 5 % en masse de la composition.
  5. Une composition détergente liquide selon la revendication 3, caractérisée en ce que le polymère défloculant satisfait à au moins un des essais de biodégradabilité choisi entre l'essai SCAS Modifié et l'essai Sturm Modifié.
  6. Une composition détergente liquide selon la revendication 3, caractérisée en ce que la viscosité du liquide est au moins inférieure à 2.500 mPas à 21 s-1.
  7. Une composition détergente liquide selon la revendication 3, caractérisée en ce que le liquide comprend de 1 à 70 % en masse de matériau détergent actif.
  8. Une composition détergente liquide selon la revendication 3, caractérisée en ce que le liquide produit moins de 10 % de séparation de phase lorsqu'il est stocké à 25°C pendant 21 jours à compter du jour de la préparation.
EP93915938A 1992-07-29 1993-07-16 Composition detergente Expired - Lifetime EP0652935B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP93915938A EP0652935B1 (fr) 1992-07-29 1993-07-16 Composition detergente

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP92306897 1992-07-29
EP92306897 1992-07-29
PCT/EP1993/001882 WO1994003575A1 (fr) 1992-07-29 1993-07-16 Composition detergente
EP93915938A EP0652935B1 (fr) 1992-07-29 1993-07-16 Composition detergente

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EP0652935A1 EP0652935A1 (fr) 1995-05-17
EP0652935B1 true EP0652935B1 (fr) 1997-09-17

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SK53294A3 (en) 1993-05-07 1995-04-12 Albright & Wilson Concentrated aqueous mixture containing surface active matter and its use
US6090762A (en) * 1993-05-07 2000-07-18 Albright & Wilson Uk Limited Aqueous based surfactant compositions
GB9315854D0 (en) * 1993-07-30 1993-09-15 Nat Starch Chem Corp Improvements in or relating to hydrotropes
EP0776965A3 (fr) 1995-11-30 1999-02-03 Unilever N.V. Compositions de polymères

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DE2316698A1 (de) * 1972-04-07 1973-10-11 Univ Toronto Polymere substanz
NL159413B (nl) * 1973-01-16 1979-02-15 Ruhrchemie Ag Werkwijze ter bereiding van afbreekbare tercopolymeren uit etheen, koolmonoxide en vinylacetaat.
GB8813978D0 (en) * 1988-06-13 1988-07-20 Unilever Plc Liquid detergents
GB8919669D0 (en) * 1989-08-31 1989-10-11 Unilever Plc Fabric-softening compositions

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WO1994003575A1 (fr) 1994-02-17
AU4570193A (en) 1994-03-03
ZA935162B (en) 1995-01-16
EP0652935A1 (fr) 1995-05-17
DE69314038D1 (de) 1997-10-23
ES2107047T3 (es) 1997-11-16
DE69314038T2 (de) 1998-01-22

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