WO1998055576A1 - Polymeric materials - Google Patents
Polymeric materials Download PDFInfo
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- WO1998055576A1 WO1998055576A1 PCT/EP1998/003005 EP9803005W WO9855576A1 WO 1998055576 A1 WO1998055576 A1 WO 1998055576A1 EP 9803005 W EP9803005 W EP 9803005W WO 9855576 A1 WO9855576 A1 WO 9855576A1
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Classifications
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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
- C11D3/3784—(Co)polymerised monomers containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
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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
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
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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
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
Definitions
- the present invention is concerned with polymeric materials which are useful for endowing desirable rheological properties to a particular class of aqueous liquid detergent compositions.
- This class of aqueous compositions comprises those which contain sufficient detergent-active material and, optionally, sufficiently dissolved electrolyte to result in a structure of lamellar droplets dispersed in a continuous aqueous 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 2444 840, whilst examples where solid particles are suspended are disclosed in specifications EP-A-160 342: EP-A-38 101: EP-A-104 452 and also in the aforementioned US 4 244 840. Others are disclosed in European Patent Specification EP-A-151 884, where the lamellar droplets are called ⁇ spherulites' . The presence of lamellar droplets in a liquid detergent product may be detected by means known to those skilled in the art, for example optical techniques, various rheometrical measurements. X-ray or neutron diffraction, and electron microscopy.
- the droplets consist of an onion-like configuration of concentric bi-layers of surfactant molecules, between which is trapped water or electrolyte solution (aqueous phase) .
- Systems in which such droplets are close-packed provide a very desirable combination of physical stability and solid- suspending properties with useful flow properties.
- the viscosity and stability of the product depend on the volume fraction of the liquid which is occupied by the droplets. Generally speaking, the higher the volume fraction of the dispersed lamellar phase (droplets), the better the stability. However, higher volume fractions also lead to increased viscosity which in the limit can result in an unpourable product. This results in compromise being reached. When the volume fraction is around 0.6 or higher, the droplets are just touching (space-filling) . This allows reasonable stability with an acceptable viscosity (say no more than 2.5 Pas, preferably no more than 1 Pas at a shear rate of 21s "1 ) . This volume fraction also endows useful solid-suspending properties.
- flocculation occurs between the lamellar droplets at a given volume fraction, the viscosity of the corresponding product will increase owing to the formation of a network throughout the liquid.
- Flocculation may also lead to instability because deformation of the lamellar droplets, owing to flocculation, will make their packing more efficient. Consequently, more lamellar droplets will be required for stabilisation by the space-filling mechanism, which will again lead to a further increase of the viscosity.
- the volume fraction of droplets is increased by increasing the surfactant concentration whereas flocculation between the lamellar droplets occurs when a certain threshold value of the electrolyte concentration is crossed at a given level of surfactant (and fixed ratio between any different surfactant components) .
- the effects referred to above mean that there is a limit to the amounts of surfactant and electrolyte which can be incorporated whilst still having acceptable product properties.
- higher surfactant levels are required for increased detergency (cleaning performance) .
- Increased electrolyte levels can also be used for better detergency, or are sometimes sought for secondary benefits such as building.
- 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 .
- the theory of function of these deflocculating polymers is that the hydrophobic chains are anchored in 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 i2 - C i5 , about the length of the surfactants in the droplet.
- the number of hydrophobic anchors per polymer molecule should be limited to one, otherwise one polymer chain could link two droplets which results in gelling of the dispersion due to bridging.
- 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 6 - C ⁇ 2 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. However, there is no example described of use of lauryl peroxide to produce a d 2 hydrophobe - terminated polyacrylate.
- telomers are not disclosed as having any efficacy in controlling the rheological properties of lamellar droplet-structured aqueous detergent liquids and indeed, aqueous detergent liquids are not mentioned at all.
- Some specific kinds of 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.
- the molecular weight of the deflocculating polymer should exceed a certain value in order to avoid building in' of the whole polymer inside the droplets.
- the applicants have discovered that the optimum molecular weight seems to be about 2500, a compromise of deflocculating efficiency and cost efficiency.
- Typical examples of the polymer disclosed in EP-A-346 995 are made by a radical copolymerization of acrylic acid and laurylmethacrylate. This results in a random distribution of lauryl chains over the polymer. As a consequence, most of the polymer molecules have one hydrophobic chain per molecule. However, a reasonable fraction of the polymer molecules have more than one hydrophobic anchors per molecule. The last fraction may give rise to a viscosity increase due to bridging.
- the polymers as disclosed in EP-A-623 679, EP-A-691 399 and US-A-5 489 397 being ⁇ end-capped' in principle have a lower fraction of polymer molecules with more than one hydrophobic anchor as compared with the polymers described in EP-A-346 995.
- the described synthesis routes of these end-capped polymers are rather limited and produce polymers which are not optimal in their performance.
- a new class of polymers constituted by the first aspect of the present invention overcomes, according to the particular new polymer in question, one or more of these drawbacks.
- 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 3 o alkyl, C 5 -C 30 alkenyl or C5-C30 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 .
- Y 1 is absent or represents a carbonyl group, an ester linkage, a hydroxy C1-5 alkyl group or a silyl group of formula (-SiR ⁇ 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 phosphinyl- linkage, but then with the proviso that W is not hydrogen.
- the group -Z- is preferably a linear, branched or slightly crosslinked 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 in water.
- the only limitations to the structure of -Z- are that the resultant polymer of formula (I) must be suitable for incorporation in 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 main 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 inter-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.
- 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.
- preferred hydrophilic backbones are: 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 de locculating 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 (QVQ 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
- the process of the invention provides a product which is stable and clear and which exhibits no gelling or product
- 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
- 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.
- Materials of the present invention preferably have a molecular weight of at least 500, more preferably at least 1000, still more preferably at least 2000 . Also, their molecular weight is preferably no more than 50,000, more preferably no more than 30,000 and especially, no more than 10,000, less than 5,000.
- any reference herein to determination of oligomer or polymer molecular weight refers to the number-averaged degree of polymerisation as determined using X H-NMR spectroscopy by comparing the intensities of the NMR peaks corresponding to the terminal methyl group (from the initiator) at ca. 0.95 ppm and the polymer backbone -CH 2 - and -CH- at 2.2 ppm, respectively.
- This so-called determination of end groups is a well-known procedure, cf . J.C. Bevington, J.R. Ebdon, and T.N. Huckerby, in NMR Spectroscopy of Polymers, R.N. Ibbett (Ed.), Chapman & Hall, Glasgow: 1993, and R.G. Garmon in Polymer Molecular Weights, Part I, P.E. Slade, Jr. (Ed.), Marcel Dekker, New York: 1975.
- the aforementioned method demands high accuracy of the integration of the NMR spectra, which is especially important if the degree of polymerisation exceeds ca. 100.
- a high-molecular weight poly (acrylic acid) was synthesised using 1 mol% of AIBN, in the absence of transfer agent.
- the molecular weight of this polymer was determined using both the end group (NMR) method and viscosimetry .
- the intrinsic viscosity of the polymer was determined to be 0.193 +_ 0.008 dl/g. From this value, the viscosity-averaged molecular weight (M v ) was calculated to be 51500 (cf. S. Newman, W.R. Krigbaum, C. Laugier, and P.J. Flory, J. Polym. Sci 1954, 14 451) .
- a second aspect of the present invention provides a method of preparing an oligomer or polymer of formula (I) as hereinbefore defined, by reacting a compound of formula (IV)
- Q 1 X 1 and Y 1 are as hereinbefore defined and Y 2 is a reactive hydrogen or a free radical, with a precursor material, in the presence of an initiator.
- reactive hydrogen is herein defined as referring to a bond heat of formation between 96 and 80 kcal/mol, preferably between 92 and 85 kcal/mol (as mentioned in ⁇ Handbook of Chemistry and Physics' , pages F223-F229, 56 ed. 1975-1976) (such as a TEMPO deriviative) .
- the precursor material is a monomer or prepolymer, containing at least one polymerizable group, said monomer or polymer being capable of forming a group of formula -Z-W as hereinbefore defined.
- the compound of formula (IV) may for example be a compound wherein X 1 is absent, Y 1 represents a carbonyl group or - COH(R 5 )- wherein R 5 is a C 1 -4 alkyl group; and if W is not hydrogen, then Y 1 can be a thia group.
- an oligomer or polymer of formula (I) may be prepared by reacting a compound of formula (V)
- Q 1 is as hereinbefore defined with a precursor material as hereinbefore defined and ⁇ -G-Q 1 is a molecule capable of cleavage to form a radical of formula -Q 1 -X 1 -Y 1 .
- a radical initiator containing the hydrophobic group Q 1 is a compound which can initiate chemical reactions by producing free radicals as mentioned in Kirk-Othmer, "Encyclopaedia of Chemical Technology, 4th edition, volume 14, page 431-460.
- Control of both hydrophobic endgroups can also be achieved by, for example, a so-called living polymerisation.
- a possible procedure involves a controlled radical polymerisation, involving TEMPO (2,2,6,6- tetramethylpiperidinyl-1-oxy) and a normal, e.g. peroxide radical initiator, as described in J.Am.Chem.Soc. 1994, 116, 11185-11186, by Craig J. Hawker.
- a compound of formula (IV), TEMPO and initiator Typically in a first step one starts with a compound of formula (IV), TEMPO and initiator.
- the product obtained from this reaction is then used in a second step by heating it in the presence of a precursor as hereinbefore defined giving a polymer with a hydrophilic backbone having on the one end a hydrophobic group and on the other the thermolabile TEMPO group.
- Heating this polymer in the presence of a hydrophobic monomer e.g. laurylmethacrylate
- a further aspect of the present invention provides an aqueous liquid detergent composition in the form of a dispersion of lamellar droplets, the composition comprising water, surfactant, a material of the invention and optionally electrolyte.
- aqueous liquid detergent composition in the form of a dispersion of lamellar droplets, the composition comprising water, surfactant, a material of the invention and optionally electrolyte.
- Such compositions are hereinafter referred to as compositions according to the present invention.
- Materials of the invention can be incorporated in such aqueous detergent lamellar dispersions to provide stable, pourable products preferably wherein the volume fraction of the lamellar phase is 0.5-0.6 or higher.
- the volume fraction of the lamellar droplet phase may be determined by the following method.
- the composition is centrifuged, say at 40,000 G for 12 hours, to separate the composition into a clear (continuous aqueous) layer, a turbid active-rich (lamellar) layer and (if solids are suspended) a solid particle layer.
- the conductivities of the continuous aqueous phase, the lamellar phase and of the total composition before centrifugation are measured. From these, the volume fraction of the lamellar phase is calculated, using the Bruggeman equation, as disclosed in American Physics, 2 ⁇ _, 636 (1935) .
- the conductivity of the total composition must be corrected for the conductivity inhibition owing to any suspended solids present.
- the degree of correction necessary can be determined by measuring the conductivity of a model system. This has the formulation of the total composition but without any surfactant. The difference in conductivity of the model system, when continuously stirred (to disperse the solids) and at rest (so the solids settle) , indicates the effect of suspended solids in the real composition. Alternatively, the real composition may be subjected to mild centrifugation (say 2,000 G for 1 hour) to just remove the solids.
- the conductivity of the upper layer is that of the suspending base (aqueous continuous phase with dispersed lamellar phase, minus solids) .
- the conductivity of the aforementioned model system at rest can serve as the conductivity of the continuous aqueous phase.
- a value of 0.8 mS.cm "1 can be used, which is typical for most systems. In any event, the contribution of this term in the equation is often negligible.
- the viscosity of the aqueous continuous phase is less than 25 mPas, most preferably less than 15 mPas, especially less than 10 mPas, these viscosities being measured using a capillary viscometer, for example an Ostwald viscometer.
- compositions of the present invention it is preferred for the compositions of the present invention to have solid-suspending properties (i.e. capable of suspending solid particles) . Therefore, in many preferred examples, suspended solids are present. However, sometimes it may also be preferred that the compositions of the present invention do not have solid suspending properties, this is also illustrated in the examples.
- the term ⁇ deflocculating' in respect of the polymer means that the equivalent composition, minus the polymer, has a significantly higher viscosity and/or becomes unstable.
- relatively high levels of the deflocculating polymers can be used in those systems where a viscosity reduction is brought about; typically levels as low as from about 0.01% by weight to about 1.0% by weight can be capable of reducing the viscosity at 21 s _1 by up to 2 orders of magnitude .
- Especially preferred embodiments of the present invention exhibit less phase separation on storage and have a lower viscosity than an equivalent composition without any of the deflocculating polymer.
- the composition may be stable or unstable.
- a phase separation occurs at a slower rate than in the flocculated case and the degree of phase separation is less.
- 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 2% by volume phase separation as evidenced by appearance of 2 or more separate layers when stored at 25°C for 21 days from the time of preparation. In the case of the compositions where the lamellar phase volume fraction is 0.6 or greater, it is not always easy to apply this definition. In the case of the present invention, such systems may be stable or unstable, according to whether or not the droplets are flocculated. For those that are unstable, i.e.
- the degree of phase separation may be relatively small, e.g. as for the unstable non-flocculated systems with the lower volume fraction.
- the phase separation will often not manifest itself by the appearance of a distinct layer of continuous phase but will appear distributed as ⁇ cracks' throughout the product. The onset of these cracks appearing and the volume of the material they contain are almost impossible to measure to a very high degree of accuracy.
- those skilled in the art will be able to ascertain instability because the presence of a distributed separate phase greater than 2% by volume of the total composition will readily be visually identifiable by such persons.
- the above-mentioned definition of 'stable' is also applicable in these situations, but disregarding the requirement for the phase separation to appear as separate layers.
- compositions according to the present invention yield less than 0.1% by volume visible phase separation after storage at 25°C for 90 days from the time of preparation.
- the amount of material of oligomer and/or polymer of the present invention in any aqueous detergent lamellar dispersion will be from 0.01% to 5.0% by weight in the composition, most preferably from 0.1% to 2.0%.
- 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 m 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) .
- Typical blends useful for fabric washing compositions include those where the primary surfactant (s) comprise nonionic and/or non-alkoxylated anionic and/or alkoxylated anionic surfactant.
- the total detergent-active 5 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
- 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.
- they may be chosen from any of the classes, sub-classes and specific materials described in 'Surface Active Agents' Vol. 1, by Schwartz & Perry, Interscience 1949 and 'Surface Active Agents' vol.
- 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 or alkyl phenols 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 .
- Suitable 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 synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C 8 -C ⁇ 8 ) 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 ⁇ 0 -C ⁇ 5 ) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C 6 - Ci ⁇ ) 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
- 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
- alkyl polyalkoxylated phosphates alkyl polyalkoxylated sulphosuccinates; dialkyl diphenyloxide disulphonates; alkyl polysaccharides and mixtures thereof.
- an alkali metal soap of a long chain mono- or dicarboxylic acid 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.
- 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.
- compositions optionally also contain electrolyte in an amount sufficient to bring about structuring of the detergent-active material.
- the compositions contain from 1% to 60%, especially from 10 to 45% of a salting-out electrolyte.
- Salting-out electrolyte has the meaning ascribed to in specification EP-A-79 646.
- some salting-in electrolyte (as defined in the latter specification) may also be 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.
- Examples of 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-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, carboxymethyloxysuccinates, carboxymethyloxymalonates, ethylene diamine-N,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, poly aleates, 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.
- 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, enzymes such as proteases, amylases, upases (including Lipolase (Trade Mark) ex Novo) and cellulases, 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 (Trade
- ICI, Gerol and Repe-O-Tex (Trademarks) ex. Rhone-Poulenc and Sokalan HP22 (Trademark) ex. BASF); 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.
- Example 1 Synthesis of mono-endcapped hydrophobically- modified poly (sodium acrylate) using a hydrophobic initiator in dioxane: solution polymerisation
- a 250 ml round-bottomed flask was loaded with 5 g of acrylic acid, 50 ml of dioxane and 0.57g of dilaurolylperoxide.
- the flask was connected to a reflux condenser fitted with a CaCl 2 -tube and was heated on an oil bath at 80°C with stirring. The reaction mixture was kept at this temperature overnight. After cooling to room temperature, the clear, slightly viscous solution was precipitated in 300 ml of pentane to remove most of the dioxane. The viscous precipitate was dissolved in dry methanol.
- the methanolic solution was slowly precipitated in a stirred solution of 3.6 g (66.7 mmol) of sodium methoxide in 100 ml of dry methanol.
- the white solid was filtered off under reduced pressure.
- the crude product was dried in vacuo at 30°C to remove most of the remaining dioxane and methanol.
- the polymer was dissolved in water to obtain a solution of about 5-10% (w/w) .
- the polymer was completely neutralised by adding sodium hydroxide until the pH was 9, and the solution was freeze-dried. In order to remove the last traces of solvent, the polymer was finely powdered and dried at 60°C over P 2 0 5 in vacuo for at least 2 hours .
- MALDI-TOFSPEC was employed to unambiguously demonstrate that the polymer molecules mainly contain only one hydrophobic chain.
- Example 2 Synthesis of mono-endcapped hydrophobically- modified poly (sodium acrylate) using a hydrophobic initiator in 2-butanone (MEK) : precipitation polymerisation.
- Example 3 Synthesis of mono-endcapped hydrophobically- modified poly (sodium acrylate) using 2-tetradecanol as a hydrophobic transfer agent in 2-butanone (MEK) : precipitation polymerisation.
- the polymer was treated with aqueous sodium hydroxide (pH 12) for 1 week. This treatment did not affect the NMR spectral characteristics of the polymer during this time, which provides evidence that no hydrolysis had taken place. Therefore, the alcohol is probably connected to the poly (acrylate) moiety through a C-O bond, which is most likely due to incorporation of the startery alcohol by a radical transfer mechanism.
- the characteristics of the polymer were as follows:
- the double-endcapped ( ⁇ , ⁇ ) -bis-dodecylthiapoly (acrylate) used as said agent for deliberate bridging of lamellar droplets can be prepared by polymerising acrylic acid in the presence of a radical initiator, and alkylsulfides as chain transfer agents.
- DP 0 is the degree of polymerisation in the absence of chain transfer agent
- [CTA] is the molar concentration of the chain transfer agent
- [AA] is the molar concentration of acrylic acid.
- DP 0 can easily exceed the value of 1000 for acrylic polymers, and so this term can be neglected here, where the desired degree of polymerisation is 40-100.
- Another way of preparing a sample with a significantly higher proportion of double-endcapped dodecyl poly (acrylate) as bridging agent for lamellar droplets is by radical polymerisation of acrylic acid in dioxan solvent using dodecanethiol as chain transfer agent and lauryl peroxide initiator.
- One method to make this polymer is as follows:
- Acrylic acid (36 g, 0.5 mol), dodecanethiol (10. lg, 0.05 mol) , dioxan (150 ml) where charged into a polymerisation reactor. After purging the reactor with nitrogen for 30 minutes, Lauryl peroxide (1.2 g) was added and the temperature was raised to 60°C. The polymerisation was carried out for 10 hours. The polymer solution was cooled to room temperature, and was neutralised with sodium hydroxide solution (20 g NaOH) . The solvent was removed using a rotary evaporator and can be re-used in another polymerisation reaction. The polymer was dissolved in water and precipitated into acetone. After purification by two more dissolution/precipitation procedures, the polymer was characterised and was ready for use in liquid detergent products .
- the weight average molecular weight (Mw) obtained by GPC and converted to polyacrylate standards is 9,000-13,000.
- Mw weight average molecular weight
- Polymer (1) is somewhat more efficient in obtaining stability than the reference polymer. Furthermore, the results suggest that polymer (2) works as a bridging and viscosity enhancing polymer. The viscosity of example 6k is much higher than the reference systems 6f and 6c.
- Oleic acid (Priolene 6907) 4.5 4.5 4.5 4.5 4.5
- Viscosity (mPa.s at 21s-l) 670 1250 1010
- polymer (1) has better deflocculating ability as the reference polymer.
- the viscosities of the products are all in the range of good consumer acceptability for a pourable liquid.
- the overall conclusion is that polymer (1) is more effective in obtaining the desired physical properties than the reference polymer.
- Viscosity (mP . a . s at 21s-l l 630 510 1380
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR9809924-8A BR9809924A (en) | 1997-06-06 | 1998-05-14 | Oligomer or polymer, process for preparing it, batch or sample of oligomeric and / or polymeric material, and liquid detergent composition |
AU77671/98A AU7767198A (en) | 1997-06-06 | 1998-05-14 | Polymeric materials |
CA002291002A CA2291002A1 (en) | 1997-06-06 | 1998-05-14 | Polymeric materials |
EP98925628A EP0986630A1 (en) | 1997-06-06 | 1998-05-14 | Polymeric materials |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB9711849.1A GB9711849D0 (en) | 1997-06-06 | 1997-06-06 | Polymeric materials |
GB9711849.1 | 1997-06-06 |
Publications (1)
Publication Number | Publication Date |
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WO1998055576A1 true WO1998055576A1 (en) | 1998-12-10 |
Family
ID=10813764
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1998/003005 WO1998055576A1 (en) | 1997-06-06 | 1998-05-14 | Polymeric materials |
Country Status (8)
Country | Link |
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EP (1) | EP0986630A1 (en) |
AR (1) | AR012919A1 (en) |
AU (1) | AU7767198A (en) |
BR (1) | BR9809924A (en) |
CA (1) | CA2291002A1 (en) |
GB (1) | GB9711849D0 (en) |
WO (1) | WO1998055576A1 (en) |
ZA (1) | ZA984689B (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000036079A1 (en) * | 1998-12-16 | 2000-06-22 | Unilever N.V. | Structured liquid detergent composition |
FR2797448A1 (en) * | 1999-08-12 | 2001-02-16 | Atofina | BIODEGRADABLE POLYACRYLATES FOR DETERGENCE |
US6762158B2 (en) | 1999-07-01 | 2004-07-13 | Johnson & Johnson Consumer Companies, Inc. | Personal care compositions comprising liquid ester mixtures |
US7074747B1 (en) | 1999-07-01 | 2006-07-11 | Johnson & Johnson Consumer Companies, Inc. | Cleansing compositions |
US7262158B1 (en) | 1999-07-01 | 2007-08-28 | Johnson & Johnson Companies, Inc. | Cleansing compositions comprising a liquid silicone and ester mixture |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0458599A2 (en) * | 1990-05-25 | 1991-11-27 | Unilever Plc | Fabric treatment composition |
EP0623670A2 (en) * | 1993-05-07 | 1994-11-09 | ALBRIGHT & WILSON UK LIMITED | Aqueous based surfactant compositions |
WO1996002622A1 (en) * | 1994-07-14 | 1996-02-01 | Basf Corporation | Stable, aqueous concentrated liquid detergent compositions containing hydrophilic copolymers |
US5489397A (en) * | 1994-03-04 | 1996-02-06 | National Starch And Chemical Investment Holding Corporation | Aqueous lamellar detergent compositions with hydrophobically terminated hydrophilic polymer |
-
1997
- 1997-06-06 GB GBGB9711849.1A patent/GB9711849D0/en not_active Ceased
-
1998
- 1998-05-14 WO PCT/EP1998/003005 patent/WO1998055576A1/en not_active Application Discontinuation
- 1998-05-14 BR BR9809924-8A patent/BR9809924A/en not_active IP Right Cessation
- 1998-05-14 CA CA002291002A patent/CA2291002A1/en not_active Abandoned
- 1998-05-14 AU AU77671/98A patent/AU7767198A/en not_active Abandoned
- 1998-05-14 EP EP98925628A patent/EP0986630A1/en not_active Withdrawn
- 1998-06-01 ZA ZA9804689A patent/ZA984689B/en unknown
- 1998-06-04 AR ARP980102613A patent/AR012919A1/en not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0458599A2 (en) * | 1990-05-25 | 1991-11-27 | Unilever Plc | Fabric treatment composition |
EP0623670A2 (en) * | 1993-05-07 | 1994-11-09 | ALBRIGHT & WILSON UK LIMITED | Aqueous based surfactant compositions |
US5489397A (en) * | 1994-03-04 | 1996-02-06 | National Starch And Chemical Investment Holding Corporation | Aqueous lamellar detergent compositions with hydrophobically terminated hydrophilic polymer |
WO1996002622A1 (en) * | 1994-07-14 | 1996-02-01 | Basf Corporation | Stable, aqueous concentrated liquid detergent compositions containing hydrophilic copolymers |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000036079A1 (en) * | 1998-12-16 | 2000-06-22 | Unilever N.V. | Structured liquid detergent composition |
US6762158B2 (en) | 1999-07-01 | 2004-07-13 | Johnson & Johnson Consumer Companies, Inc. | Personal care compositions comprising liquid ester mixtures |
US7074747B1 (en) | 1999-07-01 | 2006-07-11 | Johnson & Johnson Consumer Companies, Inc. | Cleansing compositions |
US7262158B1 (en) | 1999-07-01 | 2007-08-28 | Johnson & Johnson Companies, Inc. | Cleansing compositions comprising a liquid silicone and ester mixture |
FR2797448A1 (en) * | 1999-08-12 | 2001-02-16 | Atofina | BIODEGRADABLE POLYACRYLATES FOR DETERGENCE |
WO2001012683A1 (en) * | 1999-08-12 | 2001-02-22 | Atofina | Detergent biodegradable polyacrylates |
US6818700B1 (en) | 1999-08-12 | 2004-11-16 | Atofina | Detergent biodegradable polyacrylates |
Also Published As
Publication number | Publication date |
---|---|
CA2291002A1 (en) | 1998-12-10 |
AU7767198A (en) | 1998-12-21 |
GB9711849D0 (en) | 1997-08-06 |
EP0986630A1 (en) | 2000-03-22 |
AR012919A1 (en) | 2000-11-22 |
ZA984689B (en) | 1999-12-01 |
BR9809924A (en) | 2000-08-01 |
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