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
• • 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 is concerned with aqueous liquid detergent compositions of the kind which contain sufficient detergent-active material and, optionally, sufficiently dissolved electrolyte to result in a lamellar structure.
• aqueous liquid detergent compositions may be structured in one of two different ways to endow consumer- preferred flow behaviour and/or turbid appearance and/or of suspending particulate solids such as detergency builders or abrasive particles .
• the first way is to employ an "external structurant” such as a gum or polymer thickener.
• the second way is to form a lamellar phase "internal structure" from the surfactant (s) and water, the latter usually containing dissolved electrolyte.
• Lamellar phases 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. Lamellar phases can themselves be considered as divided into the sub-classes planar lamellar phases and lamellar droplets. Products can contain exclusively planar lamellar phases or exclusively lamellar droplets or the two forms can co-exist in the same product.
• lamellar phases in a liquid detergent product may be detected by means known to those skilled in the art, for example optical techniques, various rheometncal measurements, X-ray or neutron diffraction, and electron microscopy.
• Lamellar 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.
• Lamellar phases cause the resultant liquid product to be turbid (i.e. cloudy).
• Lamellar-structured detergent liquid which is substantially clear (i.e. substantially transparent).
• a first aspect of the present invention provides an aqueous detergent composition having a physical form selected from the group consisting of liquids, pourable gels and non- pourable gels, said composition comprising surfactant and water, which composition is structured with a lamellar phase formed of at least some of the surfactant and at least some of the water, the composition being substantially clear at 25°C.
• One means of providing the clarity afforded by the first aspect of the present invention is when the lamellar phase is in the form of lamellar droplets and a deflocculating polymer is incorporated in a composition which is already colloidally stable, even in the absence of the deflocculating polymer.
• a second aspect of the present invention provides an aqueous detergent composition having a physical form selected from the group consisting of liquids, pourable gels and non-pourable gels, said composition comprising a dispersion of lamellar droplets in an aqueous continuous phase, the composition further comprising deflocculating polymer, which composition at 25°C in the absence of the deflocculating polymer does not have a substantially higher viscosity and is colloidally stable .
• a third aspect of the present invention provides an aqueous detergent composition having a physical form selected from the group consisting of liquids, pourable gels and non-pourable gels, said composition comprising a dispersion of lamellar droplets in an aqueous continuous phase, wherein the D Vj9 o of the lamellar droplets is less than 2 micrometers.
• D V 90 90% of the volume of all droplets having a diameter smaller than stated.
• a fourth aspect of the present invention provides an aqueous detergent composition having a physical form selected from the group consisting of liquids, pourable gels and non-pourable gels, said composition comprising a lamellar phase and an aqueous continuous phase, wherein the difference between the refractive index of the lamellar phase and the refractive index of the aqueous continuous phase is such that the composition has an optical transmissivity of at least 5% as defined hereafter.
• the refractive indices of the lamellar and aqueous phases can each be adjusted by means which will be described in more detail herembelow.
• one advantageous manner of adjusting the refractive index of the aqueous phase is to increase it by dissolving a sugar therein.
• non-sugar polyols e.g. glycerol or sorbitol
• use of sugars such as those having a six membered ring structure, particularly for purposes of achieving clarity, is new.
• a fifth aspect of the present invention provides an aqueous detergent composition having a physical form selected from the group consisting of liquids, pourable gels and non- pourable gels, said composition comprising a lamellar phase and an aqueous phase, which aqueous phase has a sugar dissolved therein.
• compositions according to any aspect of the present invention have a physical form which may be that of a liquid, a pourable gel or a non-pourable gel. These forms are conveniently characterised by the product viscosity. In these definitions, and unless indicated explicitly to the contrary, throughout this specification, all stated viscosities are those measured at a shear rate of 21 s "1 and at a temperature of 25°C.
• compositions according to any aspect of the present invention which are liquids, preferably have a viscosity of no more than 1,500 mPa.s, more preferably no more than 1,000 mPa.s, still more preferably, no more than 500 mPa . s .
• compositions according to any aspect of the present invention which are pourable gels preferably have a viscosity of at least 1,500 mPa . s but no more than 6,000 mPa.s, more preferably no more than 4,000 mPa.s, still more preferably no more than 3,000 mPa . s and especially no more than 2, 000 mPa . s .
• compositions according to any aspect of the present invention which are non-pourable gels, preferably have a viscosity of at least 6,000 mPa . s but no more than 12,000 mPa.s, more preferably no more than 10,000 mPa.s, still more preferably no more than 8,000 mPa . s and especially no more than 7,000 mPa.s.
• the first aspect of the present invention requires the composition to be substantially clear.
• These measurements may be obtained using a Perkin Elmer UV/VIS Spectrometer Lambda 12 or a Bnnkman PC801 Colorimeter at a wavelength of 520nm, using water as the 100% standard.
• the clarity of the compositions according to the first (or any other) aspect of the present invention does not preclude the composition being coloured, e.g. by addition of a dye, provided that it does not detract substantially from clarity.
• an opacifier could be included to reduce clarity if required to appeal to the consumer. In that case the definition of clarity applied to the composition according to any aspect of the invention will apply to the base (equivalent) composition without the opacifier.
• structuring can be used to suspend particulate solids such as detergency builder or abrasive particles. Normally, these are so small as to simply give the composition a cloudy appearance. However, in compositions according to any aspect of the present invention, a relatively small number of large particles of functional materials could be suspended to give a pleasing visual effect without affecting the clarity of the bulk of the liquid. However, it is also possible to suspend within compositions of any aspect of the present invention, particles or speckles, purely for their visual effect. These particles, may be coloured. Such particles or speckles may for example be chosen from any of those previously known in liquid detergent products, albeit not in substantialy clear internally structured liquids.
• GB-A-1 303 810 discloses a pourable cleaning or rinsing aqueous detergent compositions m which a visually distinct component is incorporated in the form of particles of at least 500mm n diameter. These particles comprise an agent having a useful effect in the wash, encapsulated in an inert carrier such as wax or gelatin.
• the composition comprises a suspending aid such as a gum or a clay.
• GB-A-2 194 793 An example of a (non-clear) internally structured liquid which contains visible particles or speckles is disclosed m GB-A-2 194 793.
• the visible particles contain a carrier material such as sodium tripolyphosphate and/or a bentonite clay, plus a pigment.
• these speckles have an average particle size of from 1 to 1000mm (most preferably no more than 100mm), and constitute from 0.5% to 15% by weight of the composition, most preferably from 1% to 5%.
• GB-A-2 247 028 describes a lamellar structured aqueous detergent liquid which is also not substantially clear but in which are dispersed particles or droplets of a sparingly water-soluble or substantially water-insoluble dye.
• speckles or particles of a kind previously proposed for dispersion in a non-aqueous detergent liquid are described in EP-0 635 569, according to which the speckles as particles comprising a carrier material such as a bleach, builder, clay, abrasive, enzyme or biopolymer with a dye or pigment associated thereto. These particles must have a D(3,2) average particle size of from 50mm to less than 500mm
• an aqueous liquid detergent composition which are not substantially clear but which comprise a structured lamellar phase comprising surfactant, the lamellar phase being capable of suspending particulate solids and being dispersed in a continuous phase, and coloured particles suspended by said lamellar phase, wherein the coloured particles comprise a polymer shell m which is contained a core material, the coloured particles further comprising a colourant.
• the colourant of the coloured particles may be contained in the shell and/or the core.
• the colourant may comprise a dye and/or a pigment material and (as appropriate) may be admixed with, dispersed in and/or dissolved in the core material and/or the polymer shell material .
• the amount of colourant is preferably from 0.01% to 2%, more preferably from 0.1% to 1% by weight of the total of colourant plus core material.
• colourant is additionally or alternatively part of the shell, then it preferably is included at from 0.01% to 4% by weight of the total of colourant plus shell, more preferably from 0.1% to 1% by weight.
• the core material preferably constitutes from 10% to 99%, more preferably from 30% to 98% by weight of the coloured particles.
• the polymer shell may comprise any polymer which is substantially insoluble in the rest of the composition, preferred examples of suitable polymers include poly oxymethylene melamine urea (PMMU) , polyamides , cellulosic polymers , poly vinyl alcohol (PVA) , Polyurethane and carrageen (i.e. 3, 6-anhydro-d-galactan, which is a polysaccharide) , amongst others .
• suitable polymers include poly oxymethylene melamine urea (PMMU) , polyamides , cellulosic polymers , poly vinyl alcohol (PVA) , Polyurethane and carrageen (i.e. 3, 6-anhydro-d-galactan, which is a polysaccharide) , amongst others .
• Suitable core materials include diethylphthalate, alginate, and paraffin oil.
• the D(3,2) average diameter of the coloured particles is from 250 to 2,500 microns, more preferably from 300 to 2,200 microns and most preferably from 350 to 2,000 microns .
• the average density of the coloured particles is between + 35%, more preferably + 30% or + 25%, still more preferably + 20%, yet more preferably + 18 % and most + 15% of the density of the composition without the coloured particles.
• compositions according to any aspect of the present invention is to incorporate encapsulates of functional materials, e.g. enzymes, which encapsulates may or may not be coloured. However, they will normally be large enough to be distinctly visible so that the bulk of the liquid between the particles still appears substantially clear.
• functional materials e.g. enzymes
• Suitable enzyme encapsulates of the kind mentioned above are intended to effectively protect the enzyme from the adverse effect of UV radiation. Therefore it is essential that the enzyme is adequately contained in the encapsulate to prevent any significant leaking of the enzyme into the liquid detergent composition during storage i.e. preferably less than 50%, more preferably less than 40%, most preferably less than 30% of the encapsulated enzyme leaks into the liquid detergent composition while being stored for 4 weeks at 37°C.
• the enzyme encapsulate may contain polymeric material, but this is not a limiting condition. If polymers are present in the capsules, at least part of the polymeric material should not dissolve in the liquid detergent, whereas they disperse or dissolve upon dilution. Examples of synthetic polymeric materials are:
• PVA polyvinyl alcohol
• alginate e.g. Manucol DM or DH ex Kelco
• polymers are present in the capsules, they can be present as a small solid grains, either dispersed throughout the particle or preferentially located in part of the capsules, for example in the outside layer of the capsule.
• the polymers can also be present as hydrated particles, which can either be dispersed throughout the particle or located in a part of the capsule.
• Polymers can also be present in the core of the capsules, in the form of an onion ring inside the capsule or as a shell around the core .
• the enzyme capsules can also contain hydrophobic or fatty materials. Examples of this are:
• the capsules contain hydrophobic materials they should protect the enzyme against moisture.
• the hydrophobic material should envelope the enzyme solid particles or droplets which are present in the capsule.
• the capsules can contain also other ingredients:
• - density modifiers e.g. sucrose
• - structurants e.g. silica, or zeolite - fillers, e.g. talc, bentonite
• - scavengers e.g., ammonium sulphate
• the enzyme encapsulate may comprise polymeric material.
• the enzyme encapsulate comprise polymeric materials selected from the group consisting of polyvinylalcohol, polyamide, polyester, polyurea, polyurethane, epoxyresin, methylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carrageenan, alginate, gellan gum, gelatine and mixtures thereof .
• the enzyme encapsulates have a D (3,2) average diameter between 30 and 5000 microns, preferably between 200 and 3000 microns, most preferably between 500 and 2500 microns.
• the particle shape can vary from irregular to spherical; in the preferred form they should be close to spherical, but this should not be limiting.
• the enzyme encapsulates have an enzyme encapsulate' s density.- as measured in the detergent solution - of between 700 and 2500 kg/m3, more preferably between 800 and 2000 kg/m3 and most preferably between 900 and 1500 kg/m3.
• the enzyme can be distributed homogeneously throughout the particle (matrix capsule), be located in the core of the capsule (core-shell capsule) or be present in any other confined zone in the capsule, e.g. in an onion-ring shaped zone .
• the enzyme can be present in the capsules in solid form, as small particles, which can comprise pure protein or optionally a mixture of protein and other materials (optionally in a matrix with other components).
• the enzyme can also be present in the capsule in the form of small droplets of an enzyme solution, or as mixture of solid and liquid (slurry) .
• the enzyme encapsulate may comprise any detergent enzymes including protease lipase, amylase, peroxidase, cellulase or a mixture thereof.
• protease are commercially available types such as AlcalaseTM, DurazymTM, RelaseTM, SavinaseTM ex Novo Nordisk and OptimaseTM, Purafect TM , ProperaseTM ex Genencor International .
• lipase examples include LipolaseTM ex Novo Nordisk and LipomaxTM ex Genencor International.
• cellulase examples include CelluzymeTM and CarezymeTM ex Novo Nordisk, and ClazinaseTM ex Genencor International.
• amylase examples include TermamylTM ex Novo Nordisk and MaxamylTM ex Genencor International.
• the enzyme is a protease.
• the protein content is preferably in the range between 0.1 and 20%, more preferably between 0.5% and 10%, most preferably between 1% and 5%.
• the enzyme activity is from 100 GU/mg and 20000 GU/mg, more preferably between 500 and 10000 GU/mg, most preferably between 1000 and 5000 GU/mg.
• the clarity may be achieved by (when the lamellar phase comprises lamellar droplets) incorporating a deflocculating polymer.
• the dependency of stability and/or viscosity upon volume fraction is favourably influenced by incorporating into the lamellar dispersion, a deflocculating polymer comprising a hydrophilic backbone and one or more hydrophobic side- chains .
• hydrophobic chains are anchored m the outer bilayer of the lamellar droplet.
• the hydrophilic part is extended outwards.
• These hydrophilic 'brushes' are responsible for the steric stabilisation of the droplets, provided that the 'brushes' exceed a certain length.
• the optimum length of the polymer hydrophobic chain, in order to be anchored into the bilayer is in the order of C ⁇ 2 - C l , about the length of the surfactants in the droplet.
• EP-A- 346 995 defines, in practical terms, the conventional deflocculating effect as that of a polymer in a stable and pourable composition whereby the equivalent composition minus the deflocculating polymer, has a significantly higher viscosity and/or becomes unstable.
• compositions according to the second aspect of the present invention are such that the equivalent composition at 25°C, without deflocculating polymer does not have a significantly higher viscosity and is stable.
• the term "does not have significantly higher viscosity” means that a shear rate of 21s "1 , the difference in viscosity is no more than 500 mPa.s, preferably no more than 250 mPa . s .
• the term “stable” means that the composition yields no more than 2% by volume visible phase separation when stored at 25°C for 21 days from the time of preparation, more preferably less than 0.1% by volume visible phase separation when stored at 25°C for 90 days from the time of preparation.
• Compositions according to the present invention in any aspect are preferably “stable” according to these definitions.
• any composition according to the present invention comprises deflocculating polymer this may comprise one or more deflocculating polymer materials according to EP-A 346 995 and/or as recited hereinbelow.
• the amount of material of deflocculating polymer in a composition according to any aspect of the invention will be from 0.01% to 5.0% by weight in the composition, most preferably from 0.1% to 2.0%.
• EP-A-438 215 discloses preparation of acrylic acid telomers with a functional terminal group, using a secondary alcohol chain transfer agent which may, for example be a C ⁇ - C i2 monofunctional secondary alcohol.
• a secondary alcohol chain transfer agent which may, for example be a C ⁇ - C i2 monofunctional secondary alcohol.
• These materials are described as detergent additives, in particular sequestrants or anti-precipitants .
• the materials are produced using polymerisation initiators such as ditertiary butyl peroxide. In the description of various different possible initiators, there is mentioned lauryl peroxide.
• deflocculating polymers which contain only one hydrophobic moiety and which is attached to an end position of a hydrophilic chain, are disclosed in EP-A-623 670.
• deflocculating polymers comprises oligomers or polymers of formula (I) as disclosed in our unpublished international patent application WO 98/55576 Q 1 - X 1 - Y 1 - Z - W (I)
• Q 1 - represents a hydrophobic moiety
• -X 1 - and -Y 1 - are independently each absent or represent a suitable linking group
• -Z- represents a hydrophilic chain
• -W represents hydrogen or a group of formula -Y 2 -X 2 -Q 2 , each of -X 2 ,-Y 2 and -Q 2 being independently selected from the values for X 1 , Y 1 and Q 1 as hereinbefore defined.
• Q 1 represents an optionally substituted C 5 - C 30 alkyl, C 5 -C 30 alkenyl or C 5 -C 30 aralkyl group, or a hydrophobic monomer residue, such as from lauryl methacrylate or a hydrophobically modified TEMPO (2,2,6,6- tetramethylpiperdinyl-1-oxy) moiety.
• Alkyl, alkenyl or aralkyl groups most preferably have from 8 to 18 carbon atoms and are preferably straight-chained or have only limited branching.
• X 1 is absent or represents a group of formula (-CH 2 -) n where n is 1 or 2 or X 1 is phenyl .
• n is 1 or 2 or X 1 is phenyl .
• Y 1 is absent or represents a carbonyl group, an ester linkage, a hydroxy C ⁇ _s alkyl group or a silyl group of formula (-SiR 1 R 2 ) , where R 1 and R 2 independently represent -CH 3 or-C z H 5 ; or else Y 1 is a thia-, aza-, carboxy- (i.e. ester), carboxy-aza-, phosphoryl-, phosphonyl- or phosphmyl- linkage, but then with the proviso that W is not hydrogen.
• the group -Z- is preferably a linear, branched or slightly crosslmked molecular composition containing one or more types of relatively hydrophilic monomer units.
• the hydrophilic monomers themselves are sufficiently water soluble to form at least a 1% by weight solution when dissolved m water.
• the only limitations to the structure of -Z- are that the resultant polymer of formula (I) must be suitable for incorporation m an active-structured aqueous liquid detergent composition and that a polymer corresponding to the hydrophilic moiety alone, i.e. H-Z-H is relatively soluble in water, in that the solubility in water at ambient temperature and at a pH of 3.0 to 12.5 is preferably more than 1 g/1, more preferred more than 5 g/1, most preferred more than 10 g/1.
• the group -Z- is predominantly linear; more preferably the mam chain of the backbone constitutes at least 50% by weight, preferably more than 75%, most preferred more than 90% by weight of the backbone.
• the group -Z- is generally composed of monomer units, which can be selected from a variety of units available for the preparation of polymers. Examples of types of monomer units for inclusion alone or in combination in -Z- are:
• these monomer units are mono-unsaturated.
• suitable monomers are acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid, aconitic acid, citraconic acid, vinyl-methyl ether, vinyl sulphonate, vinylalcohol obtained by the hydrolysis of vinyl acetate, acrolein, alkenyl alcohol and vinyl acetic acid.
• the corresponding salts e.g. alkali metal salts such as the sodium salt, are also included.
• Cyclic units either being unsaturated or comprising other groups capable of forming mter-monomer linkages.
• the ring-structure of the monomers may either be kept intact, or the ring structure may be disrupted to form the backbone structure.
• Examples of cyclic monomer units are sugar units, for instance saccharides and glucosides; alkoxy units such as ethylene oxide and hydroxy propylene oxide; and maleic anhydride.
• Each of the above mentioned monomer units for inclusion in -Z- may be substituted with groups such as amino, ammonium, amide, sulphonate, sulphate, phosphonate, phosphate, hydroxy, carboxyl and oxide groups.
• the group -Z- is preferably composed of one or two monomer types but also possible is the use of three or more different monomer types in one hydrophilic backbone.
• hydrophilic backbones examples include: homopolymers of acrylic acid, copolymers of acrylic acid and maleic acid, poly (2-hydroxy ethyl acrylate) , polysaccharides, cellulose ethers, polyglycerols, polyacrylamides, polyvinylalcohol/polyvinylether copolymers, poly sodium vinyl sulphonate, poly 2-sulphato ethyl methacrylate, polyacrylamido methyl propane sulphonate and copolymers of acrylic acid and trimethylol propane triacrylate.
• the group -Z- may also contain small amounts of relatively hydrophobic units, e.g. those derived from polymers having a solubility of less than lg/1 in water, provided that the overall solubility of the hydrophilic polymer backbone still satisfies the solubility requirements as specified hereabove.
• relatively water insoluble polymers are polyvinyl acetate, polymethyl methacrylate, polyethyl acrylate, polyethylene, polypropylene, polystyrene, polybutylene oxide, polypropylene oxide and polyhydroxy propyl acetate.
• Preferred sub-classes of the oligomers or polymers of formula (I) include respectively, those where W is hydrogen, those where W is -Y 2 -X 2 -Q 2 , some or all of X 2 ' Y 2 and Q 2 respectively differing from X 1 , Y 1 and Q 1 and those where W is -Y 2 -X 2 -Q 2 , X 2 , Y 2 and Q 2 each being the same as X 1 , Y 1 and Q 1 .
• W is hydrogen, there is only a single hydrophobic moiety attached to one end of the hydrophilic moiety. Such materials are ideally suited as deflocculating materials. If W is a group -Y 2 -X 2 -Q 2 then there is a respective hydrophobic group at either end of the hydrophobic moiety. Such materials may be employed for deliberate bridging of lamellar droplets, e.g. to increase viscosity.
• the bridging materials having a pair of hydrophobic groups are within the ambit of the present invention.
• a predetermined blend of materials of the invention may be used, comprising one deflocculating material to control stability and one bridging material to increase viscosity in a controlled fashion.
• the bridging material has, on average, more than one hydrophobic (Q 1 /Q 2 ) groups per molecule and preferably two or more such hydrophobic groups.
• the molecular weight (Mw) of the bridging material is larger than (x.Mi + Mo), preferably larger than (x.Mi + 2Mo) and more preferably larger than 2 (x.Mi + Mo), with x being the molecular ratio between hydrophilic monomers and hydrophobic monomers, Mi being the average molecular weight of the hydrophilic groups and Mo the average molecular weight of the hydrophobic groups.
• the bridging polymer is preferably prepared using conventional aqueous polymerisation procedures, but employing a process wherein the polymerisation is carried out in the presence of a suitable cosolvent and wherein the ratio of water to cosolvent is carefully monitored so as to keep the polymer as it forms in a sufficiently mobile condition and to prevent unwanted homopolymerisation and precipitation of the polymer from the hydrophobic monomer.
• the process of the invention provides a product which is stable and clear and which exhibits no gelling or product separation on standing.
• Suitable cosolvents are selected from the group consisting of isopropanol, n-propanol, acetone, lower (Ci to C 4 ) alcohols, esters and ketones and wherein the water to cosolvent ratio is smaller than 1.5, more preferably less than 1.0, more preferably less than 0.75, and especially less than 0.5.
• sample oligomers or polymers according to the present invention will have a high weight percentage of oligomer or polymer species having a structure of formula (I), although not necessarily all of that percentage will have the same structure of formula (I).
• a preferred sample or batch of oligomer and/or polymer material the present invention may have at least 50% by weight of its total of oligomers and/or polymers having the general formula (I) as defined in claim 1, or optionally, of any preferred sub-class of polymers or oligomers of formula (I) as defined in the description or any other claim.
• This weight percentage is more preferably, in ascending order of preference, at least 65%, 70%, 75%, 80%, 85% or 90% by weight of the total batch or sample.
• the second and third aspects of the present invention apply to the subset of compositions whereby the lamellar phase comprises lamellar droplets.
• the third aspect of the present invention relies on the finding of being able to produce clarity by limiting the size of a significant fraction of the lamellar droplets, i.e. so that their D v , 90 is less than 2 microns, more preferably less than 1.0 microns, e.g. less than 0.5 microns, still more preferably less than 0.2 microns, yet more preferably less than 0.1 microns and especially less than 0.05 microns.
• the D V 90 of the droplets is defined as 90% of the volume of all droplets having a diameter smaller than that indicated.
• the actual value of D v ,9_ for a given sample may be determined by making electron microscopy pictures of the liquid detergent composition at a magnification of between 15,000 and 60,000 (preferably about 30,000) and determining the relative number of droplets of each diameter and calculating from the obtained cumulative diameter size distribution the cumulative volume size distribution or by laser light scattering particle sizers such as the Malvern Mastersizer.
• the D V/ go of the droplets can be brought to below the critical value, for example by incorporating deflocculating polymer in accordance with the second aspect of the present invention, or by using as part of the surfactant blend, so- called stabilising surfactants as disclosed in EP-A-328 177.
• Other ways of producing small lamellar droplets of the defined size include processing routes where high shear conditions are used to apply high fluid stresses. This will be explained in more detail hereinbelow in the section relating to processing.
• the fourth aspect of the present invention requires the refractive index of the lamellar phase and that of the aqueous phase to be substantially matched in such a way that the composition has an optical transmissivity of at least 5%.
• the refractive index of the lamellar phase (n lam ) can be calculated by using the refractive index of each component (n k ) in the lamellar phase and the volume fraction (v k /v lam ) by which that component is present in the lamellar phase using :
• the refractive index of the liquid detergent composition as a whole can for example be determined as follows. Light having a wavelength of 589 nm is passed through a thin layer (preferably about 1 mm) of liquid detergent composition. The angle of incidence and the angle of refraction are measured, whereafter the refractive index can be calculated by using the Snellius equation. Another, preferred method to determine the refractive index is by using internal reflection measurements, for example by using an Atago digital refractometer RX-1000 or a Bellingham and Stanley refractometer RFM91. The use of internal reflection measurements is especially advantageous for determining the refractive index for opaque systems.
• the refractive index of the corresponding aqueous phase can be measured by isolating the aqueous phase from the detergent composition (e.g. by (ultra-) centrifugation) or by separate preparation of a composition, whereby the insoluble ingredients are only added to their solubility limit and the dispersed phases are omitted.
• the difference between the refractive index of the lamellar phase and the aqueous phase is no greater than 0.02, more preferably no greater than 0.01, still more preferably no greater than 0.005 and especially no greater than 0.002.
• the refractive index of the aqueous phase can be increased and/or the refractive index of the lamellar phase can be decreased.
• the refractive index of the aqueous phase may be increased by dissolving therein materials.
• the added materials which results in a refractive index increase affect the physical stability of the system, like electrolyte or hydrotrope.
• Other relatively low molecular weight materials may not significantly affect the stability or viscosity of the composition, although there will be some effect because being an additional component of the aqueous phase, it will inevitably affect the volume fraction of the lamellar phase and/or the viscosity of the aqueous phase.
• these components are neutral non- electrolytic materials of relatively low molecular weight.
• a sugar as required by the fifth aspect of the present invention since such a material is both effective and has relatively low cost.
• water soluble non-electrolyte materials for increasing the refractive index of the aqueous phase may be selected from sugars and cellulose derivatives containing one or more hydrophilic substituents to make them water soluble.
• Suitable sugars include mono saccharides such as glucose and fructose, disaccharides such as saccharose, sucrose, lactose, maltose and cellobiose.
• Glucose syrups can also be employed. These contain mixtures of mono, di and polysaccharides . Preferably the mono and disaccharide fractions of the carbohydrate mix should be at least 50%.
• non-sugar polyols such as glycerol or sorbitol, in minor amounts in aqueous liquid detergents, for enzyme stabilisation.
• Such materials may also be employed in the compositions according to the present invention for refractive index matching but the amounts will be higher than for enzyme stabilisation, e.g. as specified hereinbelow.
• polysaccharides such as water soluble gums, e.g. guar gum, xanthan gum, arabic gum and tragacanth, because these ingredients increase the viscosity of the total system when added in appreciable amounts for refractive index matching.
• a further class of useful materials to increase the refractive index of the aqueous phase are polyols, such as glycerol and polyethylene glycol.
• the amount of water soluble non-electrolyte material in the composition will be chosen as that required to effect the substantial refractive index matching. However the minimum will amount typically be 2.5%, preferably 5%, especially 10%, by weight of the total composition.
• the maximum amount of water soluble non-electrolyte material is typically 50%, preferably 40%, especially 30% by weight of the total composition. If it is desired to specify a particular range of these amounts, any specified minimum value may be paired with any specified maximum.
• the refractive index of the lamellar phase may be reduced by choosing an appropriate surfactant or blend of surfactants.
• One suitable approach is to substantially exclude aralkyl surfactants such as alkyl benzene sulphonates, i.e the total of aralkyl surfactants should be less than 30%, preferably less than 10%, more preferably less than 5%, and especially less than 1% by weight of the total surfactants (including any soap) . Most preferably, such aralkyl surfactants are completely absent.
• a surfactant blend suitable for forming a lamellar phase without using aralkyl materials one may, for example, employ a blend of primary and/or secondary alkane sulphate or sulphonate material together with one or more nonionic surfactants.
• alkane sulph (on) ates examples include sodium and potassium alkyl sulphates, especially those obtained by sulphonating higher (C 8 -C ⁇ 8 ) , primary or secondary alcohols produced, for example, from tallow or coconut oil.
• Suitable nonionic surfactants include, in particular, the reaction products of compounds having a hydrophobic group and reactive hydrogen atom, for example aliphatic alcohols, acids, amides with alkylene oxides, especially ethylene oxide, either alone or with propylene oxide.
• Specific nonionic detergent compounds are alkyl (C 6 -C ⁇ 8 ) 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 weight ratio at the total alkane sulph (on) ate material to the total nonionic material is from 90:10 to 10:90, more preferably from 80:20 to 50:50.
• Another suitable surfactant blend for this purpose comprises one or more soaps with one or more nonionic surfactants .
• Suitable soaps include alkali metal soaps of long chain mono- or dicarboxylic acids for example one having from 12 to 18 carbon atoms.
• Typical acids of this kind are oleic acid, ricinoleic acid and fatty acids derived from castor oil, rapeseed oil, groundnut oil, coconut oil, palm kernel oil or mixtures thereof.
• the sodium or potassium soaps of these acids can be used.
• Suitable nonionic surfactants to blend with the soap are mentioned above.
• the weight ratio of the total soap to the total nonionic material is from 60:40 to 90:10, more preferably from 70:30 to 80:20.
• part or all of the detergent active material is a stabilising surfactant, which has an average alkyl chain length greater then 6 C- atoms, and which has a salting out resistance, greater than, or equal to 6.4.
• stabilising surfactants are disclosed in EP-A-328 177. Examples of these materials are alkyl polyalkoxylated phosphates, alkyl polyalkoxylated sulphosuccinates; dialkyl diphenyloxide disulphonates; alkyl polysaccharides and mixtures thereof.
• the advantage of these surfactants is that they are surfactants with a relatively low refractive index and these surfactants tend to decrease the droplet size of the lamellar droplets. Both effects have a positive effect on the clarity of the systems .
• the detergent-active material m the composition may comprise one or more surfactants, and may be selected from anionic, cationic, nonionic, zwitterionic and amphote ⁇ c species, and (provided mutually compatible) mixtures thereof.
• surfactants may be chosen from any of the classes, subclasses and specific materials described in 'Surface Active Agents' Vol. 1, by Schwartz & Perry, Interscience 1949 and 'Surface Active Agents' vol. II by Schwartz, Perry & Berch (Interscience 1958), in the current edition of
• the total detergent-active material may be present at from 2% to 60% by weight of the total composition, for example from 5% to 40% and typically from 10% to 30% by weight.
• one preferred class of compositions comprises at least 15%, most preferably at least 25% and especially at least 30% of detergent-active material based on the weight of the total composition.
• the precise proportions of each component which will result in such stability and viscosity will depend on the type(s) and amount (s) of the electrolytes, as is the case with conventional structured liquids .
• Common anionic surfactants are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
• Suitable anionics include sodium coconut oil fatty monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C 6 -C ⁇ 8 ) 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 neutralised with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reacting alpha- olefins (C_- 2 o) with sodium bisulphite and those derived from reacting paraffins with S0 2 and Cl 2 and then hydrolyzing with a base to produce a random sulphonate; and olefin sulphonates, which term is used to describe the material made by reacting olefins, particularly C10-C20 alpha-olefins, with S0 3 and then neutralising and hydrolyzing the
• the amount of water in the composition is from 5 to 95%, more preferred from 25 to 75%, most preferred from 30 to 50%. Especially preferred less than 45% by weight.
• the aqueous continuous phase may contain dissolved electrolyte.
• electrolyte means any ionic water-soluble material.
• the electrolyte not all the electrolyte is necessarily dissolved but may be suspended as particles of solid because the total electrolyte concentration of the liquid is higher than the solubility limit of the electrolyte.
• Mixtures of electrolytes also may be used, with one or more of the electrolytes being in the dissolved aqueous phase and one or more being substantially only in the suspended solid phase. Two or more electrolytes may also be distributed approximately proportionally, between these two phases.
• the terms 'salts' includes all organic and inorganic materials which may be included, other than surfactants and water, whether or not they are ionic, and this term encompasses the sub-set of the electrolytes (water-soluble materials).
• compositions of the invention 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.
• salting-in electrolyte may also be included, provided if of a kind and in an amount compatible with the other components and the composition is still in accordance with the definition of the invention claimed herein.
• Some or all of the electrolyte may have detergency builder properties.
• compositions according to the present invention include detergency builder material, some or all of which may be electrolyte.
• the builder material is any capable of reducing the level of free calcium ions in the wash liquor and will preferably provide the composition with other beneficial properties such as the generation of an alkaline pH, the suspension of soil removed from the fabric and the dispersion of the fabric softening clay material.
• water soluble inorganic detergency builders are electrolytes but any solid material above the solubility limit will normally be suspended by the lamellar phase.
• phosphorous-containing inorganic detergency builders when present, include the water-soluble salts, especially alkali metal pyrophosphates, 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.
• non-phosphorous-containmg 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, although there are restrictions with respect to the amount and volume fraction of solid particles which can be added while retaining substantial clarity.
• 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, carboxymethyloxysuccinates, carboxymethyloxymalonates, ethylene diamine-N, -disuccinic acid salts, polyepoxysuccinates, oxydiacetates, triethylene tetramine hexa-acetic acid salts, N-alkyl imino diacetates or dipropionates, alpha sulpho- fatty acid salts, dipicolinic acid salts, oxidised polysaccharides, polyhydroxysulphonates and mixtures thereof.
• Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamino- tetraacetic acid, nitrilo-triacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids and citric acid, tartrate mono succinate and tartrate di succinate.
• partly dissolved polymers include many of the polymer and co-polymer salts already known as detergency builders. For example, may be used (including building and non-building polymers) polyethylene glycols, polyacrylates, polymaleates, polysugars, polysugarsulphonates and copolymers of any of these.
• the partly dissolved polymer comprises a co-polymer which includes an alkali metal salt of a polyacrylic, polymethacrylic or maleic acid or anhydride.
• compositions with these copolymers have a pH of above 8.0
• the amount of viscosity-reducing polymer can vary widely according to the formulation of the rest of the composition. However, typical amounts are from 0.5 to 4.5% by weight.
• 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 100 ml of a 5% by weight aqueous solution of the polymer, said second polymer also having a vapour pressure in 20% aqueous solution, equal 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 6,000; said second polymer having a molecular weight of at least 1,000.
• the incorporation of the soluble polymer permits formulation with improved stability at the same viscosity (relative to the composition without the soluble polymer) or lower viscosity with the same stability.
• the soluble polymer can also reduce viscosity drift, even when it also brings about a viscosity reduction.
• improved stability and lower viscosity mean over and above any such effects brought about by the deflocculating polymer.
• the soluble polymer is especially preferred to incorporate with a partly dissolved polymer which has a large insoluble component. That is because although the building capacity of the partly dissolved polymer will be good (since relatively high quantities can be stably incorporated) , the viscosity reduction will not be optimum (since little will be dissolved) . Thus, the soluble polymer can usefully function to reduce the viscosity further, to an ideal level.
• the soluble polymer can, for example, be incorporated at from 0.05 to 20% by weight, although usually from 0.1 to 10% by weight of the total composition is sufficient, and especially from 0.2 to 3.5 - 4.5% by weight. It has been found that the presence of deflocculating polymer increase the tolerance for higher levels of soluble polymer without stability problems.
• a large number of different polymers may be used as such a soluble polymer, provided the electrolyte resistance and vapour pressure requirements are met.
• the former is measured as the amount of sodium nitrolotriacetate (NaNTA) solution necessary to reach the cloud point of 100 ml of a 5% w/w solution of the polymer in water at 25°C, with the system adjusted to neutral pH, i.e. about 7.
• the electrolyte resistance is 10 g NaNTA, especially 15g.
• the latter indicates a vapour pressure low enough to have sufficient water binding capability, as generally explained in the applicants' specification GB-A-2 053 249.
• the measurement is effected with a reference solution at 10% by weight aqueous concentration, especially 18%.
• Typical classes of polymers which may be used as the soluble polymer include polyethylene glycols, Dextran, Dextran sulphonates, polyacrylates and polyacrylate/maleic acid co-polymers.
• the soluble polymer must have an average molecular weight of at least 1,000 but a minimum average molecular weight of 2,000 is preferred.
• compositions of the present invention are substantially free from hydrotropes.
• hydrotrope any water soluble agent which tends to enhance the solubility of surfactants in aqueous solution.
• Enzymes Apart from the ingredients already mentioned, a number of optional ingredients may also be present. Enzymes, optionally together with enzyme stabilises may be incorporated. Enzymes in encapsulated form, as a visually distinct suspended component have already been mentioned hereinbefore .
• lather booster such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, fabric softeners such as clays, amines and amine oxides; 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, germicides and colourants, oily-soil release polymers, such as Poly Ethylene Terephthalate - Poly Oxy Ethylene Terephtalates or (partly) sulphonate versions thereof (including Permalose and Aquaperle (Trademarks) ex. ICI, Gerol and Repe-O-Tex
• anti-redeposition agents such as sodium carboxy methyl cellulose
• anti-dye transfer agents such as PVP, PVI and co-polymers thereof.
• These agents cause a problem in the absence of deflocculating polymer because they tend to promote flocculation of the lamellar droplets.
• examples of such agents are soluble polymers, soluble builders such as succinate builders, fluorescers like Blankophor RKH, Tinopal LMS, and Tinopal DMS-X and Blankophor BBH as well as metal chelating agents, especially of the phosphonate type, for example the Dequest range sold by Monsanto.
• Compositions of the invention may be prepared by any conventional method for the preparation of liquids 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 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.
• the manner of preparation and of treatment post processing can materially influence the optical transmittance and clarity of the composition produced.
• high shear conditions preferably at least 10,000s "1 ) to apply high fluid stresses and facilitate the production of small lamellar droplets is preferred for the second and third aspects of the invention.
• the high shear conditions (where "shear” refers to deformation rates involving either or both shear or extensional deformations) can be applied during the preparation, for example during the formation of lamellar droplets stage.
• a sixth aspect of the present invention provides a process for preparing a composition according to any one or more aspects (but especially the second and or third aspects) of the present invention, the process comprising mixing at least some of the ingredients of the composition at a shear rate of at least 10,000s "1 and then admixing the resultant composition with any remaining ingredients.
• Higher viscosity mixes can also be generated by withholding some of the process water in order to apply the high shear step to a concentrate of the final product followed by a dilution step, for example as part of the process described in the specification of patent application WO 96/20270.
• the high shear conditions can be applied to the final composition after preparaton.
• High shear may be applied by a static device, for example a shear valve such as a Saunders diaphragm valve.
• a dynamic device such as a dynamic mill. Examples of such devices include those manufactured by Silverson, Fryma or Janke & Kunkel and that described in the specification of patent application WO 96/20270.
• the shear device should be located in line in order to minimise aeration of the composition which would detract from the optical transmittance and clarity.
• a de-aeration step such as centrifugation, can be incorporated into the preparation.
• Examples 20-22 different sugars + Silverson (shear rate ca 50,000 sec ""1 ). This further illustrates the benefits of shearing and also illustrates the benefit of higher mono- and di-saccharide contents in commercial 'glucose' syrups. It also demonstrates that shearing in the absence of sugar addition (partial refractive index matching) is not sufficient .
• Cerestar 01632 - of the solids content 38% is monosaccharide (dextrose) , 37% disaccharide (maltose) and 25% tri- and poly saccharides
• Example 23 Device in Example 23 is an example of the dynamic mixer described in patent application WO 96/20270. This is a cavity transfer mixer modified by axial movement of the rotor with respect to the stator. This has the function of allowing combination of significant shear and extensional flow fields by arranging the cavities such that the cross-sectional area for flow of the liquid successively increases and decreases by a factor of at least 5 through the apparatus. Results for Cl represent averages of different machine operating conditions.
• Examples 24-26 are examples generated via a static shearing device. This is the Model “A” Sonolator, manufactured by Sonic Corporation. Compositions were pumped at backpressures ca 150 bar through a circular nozzle (orifice) of diameter 0.032 cm 2 at 30°C.
• the second comparative example shows lower level of shear providing insufficient increase in transmittivity .

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