Title of Invention

POROUS BODIES AND METHOD OF PRODUCTION THEREOF

Abstract Water dispersible or water soluble porous bodies comprising a three dimensional open-cell lattice containing (a) 10 to 95% by weight of a water soluble polymeric material and (b) 5 to 90% by weight of a surfactant, said porous bodies having an intrusion volume as measured by mercury porosimetry of at least about 3 ml/g with the proviso that said porous bodies are not spherical beads having an average bead diameter of 0.2 to 5mm.
Full Text T3111 / C
FORM - 2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See Section 10 and Rule 13)
POROUS BODIES AND METHOD OF PRODUCTION THEREOF
UNILEVER PLC, a British Company and having its registered office at Unilever House, Blackfriars, London EC4P 4BQ, United Kingdom
The following specification particularly describes the invention and the manner in which it is to be performed.

" Printed: 20/10/2005.
DESCAMD; - 1 -
POROUS BODIES AND METHOD OF PRODUCTION THEREOF
The present invention relates to water soluble or water dispersible porous bodies and to methods of producing such porous bodies.
5
Copending international-patent-application PCT/GB03/03226 (assigned to the present applicants) describes the formation of porous beads comprising a three dimensional open-cell lattice of a water-soluble polymeric material with an average bead diameter in the range 0.2 to 5mm.
10 It is an object of the present invention to provide highly porous bodies which disperse rapidly when contacted with water. It is a further object of the invention to provide a simple and effective method for producing such porous bodies.
In accordance with a first aspect of the invention, there is provided water dispersible or water soluble 15 porous bodies comprising a three dimensional open-cell lattice containing
(a) 10 to 95% by weight of a water soluble polymeric material and
(b) 5 to 90% by weight of a surfactant,
said porous bodies having an intrusion volume as measured by mercury porosimetry (as hereinafter described) of at least-abet*3 ml/g
20 with the proviso that said porous bodies are not spherical beads having an average bead diameter of0.2to5mm
Preferably the porous bodies of the present invention contain 10 to 80% by weight of the water soluble polymeric material and 20 to 90% by weight of the surfactant More preferably the porous
2 5 bodies of the present invention contain 20 to 70% by weight of the water soluble polymeric material
and 30 to 80% by weight of the surfactant
The polymeric material is a material which would be considered as "water soluble" by those skilled in the art i.e. if it forms a homogeneous solution in water. In general terms water soluble polymers
3 0 possess pendant polar or ignitable groups (e.g. -C=0, -OH, -N(R1)(R2) in which R1 and R2 which
may be the same or different are independently H or (C1 to C4)alkyl, -N(R3)(R4)(R5)+ which R3 ,R4 and R5 which may be the same or different are independently H or (C1 to C4)alkyl, -CON(R6)(R7) in which R6 and R7, which may be the same or different are H or (C1 to C4) alkyl, -CH2CH2O-, -CO2H or salts thereof, -SO3H or salts thereof groups) on a backbone chain which may be

AMENDED SHEET



Printed 20/10/2005 DESCPAMD 04804369
AMENDED SHEET
It is also important for the operation of the present invention that the porous bodies dissolve or disperse quickly so that the materials contained within the lattice are dispersed quickly when the porous bodies are exposed to an aqueous medium. It has been found that when water soluble polymeric materials are incorporated into the porous bodies of the present invention, the time it
5 takes for the polymeric material to dissolve or disperse may be significantly reduced. The nature of the lattice should be such that the dissolution or dispersion of the porous bodies preferably occurs in less than three minutes, more preferably less than two minutes, most preferably less than one minute.
10 Examples of water soluble polymeric materials include:-
(a) natural polymers (for example naturally occurring gums such as guar gum or locust bean gum or a polysaccharide such as dextran or colluloeoj
(b) cellulose derivatives for example xanthan gum, xyloglucan, cellulose acetate, methytoellulose, methyethylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, hydroxypropylcellulose,
15 hydroxypropylmethylcellulose (HPMC), hydroxypropylbutylcellulose, ethylhydroxyethylcellulose,
carboxymethylcellulose and its salts (eg the sodium salt SCMC), or
carboxyrnethylhydroxyethylcellulose and its salts (for example the sodium salt);
(c) homopolymers of any one of the monomers listed in Table 1 below;
d) copolymers prepared from two or more monomers listed in Table 1 below;
2 0 (e) mixtures thereof
Table 1
vinyl alcohol,
acrylic acid,
methacrylicacW
25 acrviamide,
methacryiamide
acryiamide methylpropane sulphonates
aminoalkylacrylates
aminoalkylmethacrylates
30 hydroxyethylacrylate
hydroxyethyimethylacrylate
vinyl pyrrofidone
vinyl imidazole
vinyl amines
35 vinyl pyridine
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ethylenegrycol
ethylene oxide
ethyleneimine
styrenesulphonates
5 ethyleneglycolacfytetes
ethylenegJycol methacryiate
When the polymeric material is a copolymer may be a statistical copolymer (heretofore also known as a random copolymer a block copolymer, a graft copolymer or a hyperbranched
10 copolymer. Comonomers other than those listed to Table 1 may also be included to addition to those listed if their presence does not destroy the water soluble or water dispersible nature of the resulting polymeric material.
Example of suitable homopolymers include polyvinylalcohol, polycrylic acid, polymethacrylic acid,
15 polyacrylamldes (such as poly-N-isopropylacrylamide), polymethacrylamide; polyacrylamines,
polymethylacrylamines, (such as polydimethylamino-ethylmethacrylate and poly-N-
morpholinoethylmethacrylate, polyvinylpyrrolidone, polyvinylimidazole, polyvinylpyridine, polyethyleneimine and ethoxylated derivatives thereof.
20 The surfactant may be non-ionic, anionic, cationic, or zwitterionic and is preferably solid at ambient
temperature. Examples of suitable non-ionic surfactants include ethoxylated triglycerides; fatty alcohol ethoxylates; alkylphenol ethoxylates; fatty acid ethoxylates; fatty amide ethoxylates; fatty amine ethoxylates,- sorbitan alkanoates; ethylated sorbitan alkanoates; alkyl ethoxylates; pluronics; alkyl pofygtocosides; stearol ethoxyiates; alkyl pdygrycosides. Examples of suitable anionic
25 surfactants include alkylether sulfates;alkylether carboxylates; alkylbenzene sulfonates;alkylether
phosphates; paraffin sulfonates; alkyl sulfonates; soaps; alkyl sulfates; alkyl carboxylates; alkyl phosphates; paraffin sulfonates; secondary n-alkane sulfonates; alpha-otefin sufonates; isethionate sulfonates. Examples of suitable cationic surfactants include fatty amine salts; fatty diamine salts; quaternary ammonium compounds; prosphorium surfactants; sulfonium surfactants; sulfonxonium
30 surfactants & Examples of suitable zwitterionic surfactants include N-alkyl derivatives of amino acids
(such as glycine, betaine, aminopropionic acid); imidazoline surfactants; amine oxides; amidobetaines Mixtures of surfactants may be used

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The bulk density of the porous polymeric bodies is preferably in the range of from about 0.01 to about 02 g/cm3, more preferably from about 0.02 to about 0.09 g/cm3, and most preferably from about 0.03 to about 0.08 g/cm3.
5 The porous bodies of #« present invention may be formed by freezing an intimate mixture (for example an emulsion) of the polymeric material and the surfactant in a liquid medium and freeze drying the resulting frozen mixture.
The porous bodies of the present invention disperse when exposed to an aqueous medium. By
10 including a water soluble polymeric material and a surfactant in the lattice of the porous bodies
porous bodies are formed which dissolve or disperse rapidly in aqueous media The polymeric material, surfactant and any other components carried in the porous bodies will therefore become dispersed/dissolved when the bodies are exposed to an aqueous medium. The provision of the porous bodies of the present invention facilitates the dissolution or dispersion of the materials
15 contained in the porous bodies and the dissolution/dispersion is more rapid than is observed when
the same materials are used but are not in the porous bodies of the present invention. The porous bodies of tine present invention may therefore be used to f facilitate the dissolution or dispersion of polymeric materials or surfactants. For example, surfactants may be Incorporated into porous bodies of the present invention which will disperse at lower temperature and/or more easily than
20 possible up to now. This is particularly beneficial when the surfactant is being used for defeats cleaning tasks such as for cleaning delicate fabrics or where only cold water is available for use in the cleaning process.
The present invention also includes, in a further aspect, solutions or dispersions comprising wafer
25 soluble polymeric materials and surfactant formed by exposing the porous bodies of tine present invention to an aqueous medium
The porous bodies of fine present invention may include within the lattice hydrophobic materials
which will be dispersed when the polymeric bodies are dispersed in an aqueous medium.
30 The hydrophobic materials may be incorporated into the lattice by dissolving them in the
discontinuous oil phase of an oil-in-water emulsion from which the lattice is made.It has been found
that the dispersion into an aqueous medium of hydrophobic materials contained within the porous bodies of the present invention is much improved when the porous bodies are exposed to the aqueous medium.

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The present invention also includes, in a further aspect, solutions or dispersions comprising water soluble polymeric materials, surfactant and a hydrophobic material formed by exposing the porous bodies of the present invention having the hydrophobic material contained therein to an aqueous medium.
5
There are many instances to personal care products such as deodorants skin and hair cleaning or care products or m household products such as laundry cleaning and care products or household cleaning or care products for hard and soft surfaces where a is desirable to administer hydrophobic materials in an aqueous environment Because of the hydrophobic nature of these materials they
10 are often reluctant to disperse in an aqueous environment The use of the porous bodes of the present invention felicitates this dispersion and in many cases enables hydrophobic materials to be dispersed more effectively than previously.
It may be required to disperse fie hydrophobic materials at the point where the product is being
15 used. In this case the porous bodies of the present invention will be contained in the product until it is used by exposing it to an aqueous environmental, at which time the water-soluble/dispersible of the porous body will break down releasing the hydrophobic material

The porous bodes of the present invention may be used to introduce hydrophobic materials into
20 products, for example, liquid products during the manufacture of the products. In this case
lattice of the porous bodies of the present invention will break down when the porous bodies contact an aqueous environment during manufacture releasing the hydrophobic material in a form in which it can be more readily incorporated into the product being manufactured.
25 The porous bodies of the present invention may be used to transport materials to sites where they
can be incorporated into products. By converting liquid products into porous bodies the need to
transport large amounts of Squids can be avoided resulting in significant cost saving and safer
transport of materials which are potentiatyha2ardous when transported in a liquid form. Materials
which would be potentially unstable if stored or transported in liquid form may incorporated into
30 the porous bodies of the present invention and stored or transported with Jess risk of degradation.
The incorporation of potentially unstable hydrophobic materials, for Example vaccines, vitamins or perfumes, into the porous bodies of the present 'invention may protect them from degradation during storage prior to use.

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Some specific examples of products h which the porous bodies of t)e present invention may be used are given below. These are given as examples only and are not intended to limit the applicability of the present invention Those skilled in the art will however realise that the porous bodies of the present invention will have utility to other areas not specifically exemplified herein.
5
Hydrophobic materials that are released from tie porous bodies of the present invention at the time of use may include:-
• antimicrobial agents, for escarp
10 phthallmoperoxyhexanoic acid (PAP) quaternary ammonium compounds, colloidal silver, zinc
oxide.
• antidandruff agent for example: zinc pyrithione
• skin lightening agents for example4-ethylresorcinol
• fluorescing agents for example: 2,5-bis(2-benzoxazolyl) thiophene for use on fabrics(such as
15 cotton, nylon, polycotton or polyester)n laundry products
• skin condition agents, for example cholesterol
• antifoaming agents for example isoparrafin
• hair conditioning agents for example quaternary ammonium compounds protein hydrolysates peptides ceramides and hydrophobic conditioning oils for example hydrocarbon oils such as
20 paraffin oils and/or mineral oils ,fatty esters such as mono-di- ,and triglycerides>silicone oils
such as polydimethylsiloxanes (e.g. dimethicone) and mixtures thereof
• fabric condtioning agents for example quatemary ammonium compounds having 1 to 3,
preferably2 optionally substituted (C8-C24)alk(en)yl chains attached to the nitrogen atom by
one or more ester groups; hydrophobic monoparticles
25 sucrose tetra-tallowater ;silicones for example polydimethylsiloxane
• thickening agents for example hydrophobically modified cellulose ethers such as hydroxyethylcelluloses
• dyes for example dyes intended to change the colour of fabrics, fixes, skin or hair.
• UV protecting agents such as sunscreen for example octyl methoxycinnamate (Parsol MCX)
30 butyl methoxydibenzoylmethane (Parsol 1789) and benzophenone-3(Uvinal M-40),ferulic acid
• bleach or bleach precursors for example 6-N^thaBrnidopercKyhexanoic acid (PAP) or
photobleaching compounds, Dispersion the bleach from he porous bodies of he present
invention results in the bleach being more finery dispersed and reduces the spot damage seen
when larger particles of the bleach contact a fabric

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• antioxidants for example hydrophobic vitamins such as vitamin E,retinal,antiodants based on
hydroxytoluene such as hganoix or commercially available antioxidants such as the trollax series.
• Insecticides pesticides herbicides that are stored as solid composition before use but which
5 are made up into IquJd^spray^aitoamr^ or crops
• periunTescfflavouriigscrpreajrsorslhereto
• pharmaceuticaly or veterinary acfive materials. Triere Is a need for Dharmaceufical
compositions which cai belaid
with a clrtok such as water. These corrposJBorehteradwitti the moisture h tie oral cavty to
10 release the ac^ ingredient which Is tienligested by tie consumer. Byhcorporatihgflie
pharmaceu*^ or veterinary active mofecute h ^ porous borJes of the piBsertirrventfon, pharmaceutical compositions which meet trfc need can be prepared.
• hasimilarwaytothatrJescrfcedarxAerjhann^
be formulated so that they release the active material toto the nasal, occular,rArirnonary or
15 rectal cavities or on thesWn where they may act topSralry or they may be absorbed
IransdermaDy to act svstemfcalry
• By using the appropriate rx>lymeric material tote
invention, porous bodies can be made fiat rernahtotactur>at>eccfxit)orer/cr example
temperature c*pH)diange to trwseurKterwhWidfeper^^ Thusdspersbncanbe
20 delayed unS a certain temperature has been reached or una the r^ has changed to a suitable
value such as would occur as tie porous bodies pass down theGltract TheacUryintheGI tract reduces down the Gl tract and porous bodes which dfepersehydrcphobfcactfvesonry when the porous bodes are exposed to higher pH condfflons enabte pharmaceuticaly or veterinary active materiab to be released onryh the intesttoehavtog passed ftrough the
25 stomach intact
Bcamptes of situations where f>e porous bodes of the present tovertfonareusedtobcorporatea hydrophobic material toto a product during The marwfecturerftoatproclLKiindude:-
30 • the introduction of hydroprK)Kc materials sucli as fluorescers^
polymers for example hyoVophobicaliy modified poryacrylates, silicones, hyclrocoobjcaly modified rx)fyv»iylpynrofidone, sulpha alkyf polysaccharides, Jaguar and JR polymers; fetty alcohols or acids; dyes for example shadhg dyes or black dyes for colour recovery into laundry products.

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• the use of porous rjodiesaccoinrthg to thepresertiwentjoncontahtoghyclr^^ manufacture of water soluble inkjet compositions.
• theiitrociurjkxicfrxrousbcxjfesa^^ nrenufacturer to produce a siigte base fc^^
5 may be totrajuced by the ijsec/the aporop^
• theuseofrxroijslxxjtesrontafti^
lattice breaks down to form a latex. The use of such latexes corrtaWng appropriate
hydrophobic polymers ofeposled onto febrfc imparts crease re^
thefebria
10
The porous bodies of the present hverrtfon may hdude within the lattice, water soluble materials which will be dispersed when the polymeric bodies are dispersed h an aqueous rnerJurrt The water soluble materials may be incorporated Wo f^lat6(»bycfissoK%)gtt)emto1reiq^merJum from which they are made. Examples of suitable water solubto materials toclude:-
15 Water soluble vitamins such as viamh C; water soluble fluorescers such as 4,4-bis(sulfostyry0btohenyl dfeodium salt (sob under the trade name Tiiopal CBS-X; activated aluminum chforohydrate; transition metal complexes used as bleaching catalysts; water soluble polymers such as polyesters isopbthafc addX gerol, xanthan gum, or poryacrytetes; cBethylenetriamtoepentaacetfc acid (DTPA); primary and secondary alcohol sulphates containing
20 greater than C8 chain tengtfi fix example the materials IOTKAWI corrinerrja^ as OXXJPAS or mixtures thereof
The porous bodies of the present hvenfion may hdude within the lattice, materials which wi be dispersed as very smal particles when the polymeric rxxies are dispersed h an aquecusmedtom. 25 These materials iriay be iocorrxrated into
medium from which the rx>rous bodies are made. If fie partfctes are less tianl micron, preferably less than 0.5 micron and they are roorporated Mo skincare products Then the particles wi not be felt by the user as the dispersed porous bodies are appied to t>e skto.
30 The intrusion volume of the porous polymeric bodies as measured by mercury porosimetry (as hereinafter described) of each polymeric bodies is at least about 3 ml/g, more preferably at least about 4 ml/g, even more preferably at least about 5m!/g, and most preferably at least about 6 ml/g. For example, the intrusion volume may be from about 3 ml/g to about 30 ml/g, preferably from about 4 ml/g to about 25ml/g, more
35 preferably from about 10 ml/g to about 20ml/g. Intrusion volume provides a very good

PriritVdi20/J0/20d5j DESGRAWDi ^04804363

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porous bodies of the present invention.-The polymeric porous bodies may be in the form of powders, beads (but not spherical beads having an average bead diameter of 0.2 to 5 mm) or moulded bodies. Powders may be prepared by the disintegration of polymeric porous bodies in the form of beads or moulded bodies either before or after freeze-drying. 5
In accordance withanother aspect of the presentinventionrthere is provided a method for water dispersible or water soluble porous bodies comprising a three dimensional open-cell lattice containing
(a) 10 to 95% by weight of a water soluble polymeric material and 10 (b) 5 to 90% by weight of a surfactant,
said porous bodies having an intrusion volume as measured by mercury porosimetry (as herein described) of at least ■abet* 3 ml/g
with the proviso that said porous body is not a spherical bead having an average bead diameter of 0.2 to 5mm 15 comprising the steps oft
a) providing an intimate mixture of the polymeric material and the surfactant in a liquid
medium b)
providing a fluid freezing medium at a temperature effective for rapidly freezing the
liquid medium;
20 c) cooling the liquid medium with the fluid freezing medium at a temperature below
the freezing point of the liquid medium for a period effective to rapidly freeze the Squid medium; and (d) freeze-drying the frozen liquid medium to form the polymeric bodies by removal of the liquid medium by sublimation.
2 5 The intimate mixture of the polymeric material and the surfactant in the liquid medium may be an oiMn-water emulsion comprising a continuous aqueous phase containing the polymeric material, a discontinuous oil phase and the surfactant
When the porous body is to be in the form of a powder the cooling of the liquid medium may be 30 accomplished by spraying the liquid medium in atomised form into the fluid freezing medium. When the porous body is to be in the form of beads the cooling of the liquid medium may be accomplished by dropping drops of the liquid medium into the fluid freezing medium. Porous bodies in the form of moulded bodies may be made by pouring the liquid medium into a mould and cooling the liquid medium by the fluid freezing medium. In a preferred process of the invention to
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make moulded bodies, the IquW roedtom is poured toto a pre-cooted mould surrounded by fluid freezing medura
The frozen Squid medium may be freeze-dried by exposing fie frozen Squid merJum to high 5 vacuura The ccrxSfore tote used v^
be appBed and tie time taken should be such fiat al tie frozen fiquW rneclum present has been rernovedbysubSrnatioa In the case of moulded porous polymeric bcdes the freeze dying may take place will the frozen Bo^medumsH^
rnay be removed frcm trie rrxxdd and fi^^ Thefreeze-dryhg
10 step nrey be perilled fcr up to arourri 72 hoMsh invention.
The above process preferably uses an oWrvwater emulsion which cornprises a continuous aqueous phase wrtti the polymeric material dissolved thereto, a dfeconttouous oi phase and the 15 surfactant which is to be inccirporated toto tf^
as an emulsffier for the emulsion. Preferably, The polymeric material is present in the continuous phase to a concentration of about 1% to 50% by weight Even more preferably, the polymeric material is present in the continuous phase to a concentration of about 3% to 10% by weight
20 Surfectontssufebtefcruseasernufcliersto
toe range 8 to 18. It is preferred fiat fie surfactant is present to toe Squid medium to a concentration cfabcut 1%toabout 60% by webjitfc^
Squid medium to a concentration of about 2 % to about 40 % by weight and a yet more preferred concentration Is about 5% to about 25% by weight
25
The cSscontinuous ol phase of toe cnHn-water emulsion preferably comprises a material which is jrnrnJsdbte wito thecontinuous phase, which freezes at a temperature above toe ten^erature which is effective for rapidy freeztog toe Squid medium andwriictiisremcvabtebysubBrriaticnc^rtogfie freeze drytog siaga The cfisconttouous oB phase of the emulsion may be selected from one or
30 more from the foBowtog group of organic sotvents:-
aHcanes such as heplane, n-hexane, isooctane, dodecane, decane; cyclic hydrocarbons such as toluene, xytene, cycfohexane; halogenated alkanes such as dfchloromethane, dichoroethane, trichloromethane (c^ioroform), fbordrxhtorarnethane and tetrachloroethane; esters such as ethyl acetate;
3 5 ketones such as 2-butanone;

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elhers such as dfethyl ether;
volatile cycle sBcones such as cydometfcone;
aind mixtures tnereof
5 Preferably, flie organic so/vent comprises fomatart 10% to alx^
preferably from about 20 % to about 60 % vAr. A preferred solvent Is (^clcftexane as tie freeziig poht of cyctohexane Is higher ten fiat of vyalerandfiiespecifcheatrapacayforcycWiexanefe much Jovverlnan that of water. Tbfehduces rapid freeztog of tieemulsfori.
10 in theprocess of the invention the fluid freeztog medtom is pneferaMy^
Preferably, the fluid meoTum is at a temperature below the freezing point of all of the components and is preferably at a much tower temperature to feciteterapW freezing. The fluid freezing meo\im is preferably a liquified substance which is a gas or repotr at standard temperature arxi pressure. The Iquified fluid freezing mecfum may be at its boing point during the freezing of tie Iquid
15 medium or it may be cooled to below te boing poht by external cooftig means. The fluid freezog medium may be selected from one or more of toe foBowing group; Iquid air, Bquid nitrogen (b.p. -196'C), iquid ammonia (b.p. -33*C), IquBed noble gas such as argon, iquefied hatogenated hydrocarbon such as trfchforoethytene, chloofluc>rc 20 also be used as toe fluid freezing medum. Bcamples of suitable mixtures include chtaroformor
acetone arxisc>Bd fluid medium is removed during freeze drying preferably uxier vacuum arxi may be raptured for reuse. Due to the very tow boing temperature, inertness, ease of expulsion and economy, liquid nitrogen is tie preferred fluid freezing medtora
25
The emulsions are typicaly prepared under corxftbns which are vvetfac^
art, for example, by using a magnetic stirring bar, a homcgenrzer,c>rarototorrnechanical stirrer.
The porous polymeric bodies procbcedusualycc)rnprise of two types of pores which are produced 30 during the freeze drying step. One is from tie subBmatico c* soM ice. This pore structure can be varied by varying the polymer, the polymer molecular waght, the polymer concentration, toe nature of the discontinuous phase and/or the freezing temperature. The other kind of pore structure results from toe sublimation of the oil phase material whereby the oil droplet structure found in the frozen porous bodies are replicated in the porous bodies.

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The metood for producing porous bodes accordhg to the present invention, wil now be more particularly described, by way of example only, wNh refererK»tot)eaccc In the Examples tiat foBow t)e Hrusfon volume and bulc density are measured by mercury 5 porosimetry as describedbetow and The dfesoJuKmttne is measured as descrtoedbetow.
Mercury porosimetry
Pore intrusion volumes and bulk densities were recorded by mercury Intrusion 10 porosimetry using a Mfcromeritics Autopore IV 9500 porosimeter over a pressure range of 0.10 psia to 60000.00 psia. Intrusion volumes were calculated by subtracting the intrusion arising from mercury interpenetration between beads (pore size > 150//m) from the total intrusion.
15 Dissolution Time
A weighed sample of the polymeric bodies was stirred gently with water until the stirred mixture was clear to the eye. The time at which the mixture became clear to the eye was recorded as the dissolution time
20
Example 1
An experiment was conducted to order to produce a highty porous, rapidryclssoKtgvvater-soW!>le powder in which the polymeric material is polyvinyl alcohol The powder contained 50% wAv porymerarri 50% wAv surfactant This powder was prepared by fteedngan atomised oHvwater
25 emulsion to Iquid nitrogen. The emulsion comprised an aqueous continuous phase containing polyvinyl alcohol and a Discontinuous phase cornpristog cycJohexana Soclum dodecyi sulphate (SDS) was used as the surfactant
A 5% aqueous solution of polyvinyl alcohol was prepared by adding polyvinyl alcohol (PVA ex 30 AJcto,^=9000-10XW,80%hydrorysecO to
stirred with a type RW11 Basic IKA paddte stirrer, and SDS (0.1g - 98%, ex Aldrfch) was added followed by cyclohexane (0.5ml) to form an emulsion having 20% v/v of discontinuous phase. The emulsion was sprayed into liquid nitrogen from an airbrush. The frozen emulsion was placed in a freeze-drier overnight

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The intrusion volume and he buk density were measured using mercury porosimetry as described above. The dfesoWion time for the powder (100mgh2nr4vvaterat20'Csfirredat250jpm)isgrven in Table Z
5 Tabte2

% Discontinuous Intrusion Volume Buk density Dissolution tine at
phase am) (Qfrnl) 8*C (minutes)
20 1&21 0.0684 4.08
For comparison the polyvinyl alcohol as suppled from the manufacturer had a Dissolution time of about 23 minutes and the sold obtained by freeze drying a 3% aqueous solution of the polyvinyl 10 alcohol had a Dissolution time of 12 minutes. The formation of the porous powders therefore enables t)e polyvinyl alcohol to be dfesorved h an aqueous medum much more rapidly than fe seen win the untreated polymer.
Example 2
15 An experiment was COTKJIK^ in c>rcier to prcriire
powder ri which 1he polymeric material is pofyethylenegfycol (PEG). The powder contained 66.7% W7to polymer and 33.3% wAv surfactant This powderwas prepared by freezing an atomised oWv water emulsion ii (quid nitrogen. The emulsion comprised an aqueous continuous phase containing PEG and a discontinuous phase comprising cydohexana Soofum dodecyi sulphate
20 (SDS) was used as the surfactant
A10%ao^eoussolu8OTcfPH3waspfeparedbya* to
deionised water. Asan^of1hesolu6m(2m0wasstiTedw}fo^ stirrer,and SDS (0.1g-96%, ex AMrich) was ao^ folov^ by cydoliexare ^ 25 emulsion having 75% vA/ of discontinuous phasa The emulsion was sprayed into liquid nitrogen using an air-brush. The frozen emulsion was placed h a freeze-drier overnight
The solid obtained by freeze drying a 10% aqueous solution of the PEG had a bulk density of 0.1034 o/rnl whereas the polymeric body prepared in Example 2 had a buko^fy of 0.0500 g/ml.

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Example 3
An experiment was conducted h order to produce a highly porous, rapidry dissolving powder h which t>e polymeric material issooTum carboxymethylceBulose (SCMCX The bodies contain about 37.5% polymeric material and about 62.5 %wto of surfactant This body was prepared by freezing 5 an ol-in^^ater enriursjco h lo^ rirlrogea Tn^
confafthg sodium raitrocymethyteiilose and a drsoonfihuous phase comprising cyctohexana Socfium dodecyl siibhate (SDS) was used as tie surfactant
A 3% ac^jeois solution of SCMC was prepared byaddhgSCMC(SCMC ex AWrfch,Mi»=90000) 10 to deionised water. A sample ofthesorufion^ml) was sftTedwrtti a type RVV11 Basic IKApaddte
stfrrer.and SDS(0.3g-98%,exAldrich)wasadc^tcflowedbysufl^^
emulsion having 40% vsV of dfeconfihuous phase. A sample with no cyclohexane (0%
ofecontinuous phase) was also prcduosdi) a s^
nitrogen usiig an air-brush. The frozen emulsim was placed h a freezB The dissolufion time for tie bodies (lOOmg h 2ml water at 20*C stirred at 250rpm) are given h
Table 3.
Table 3 20

% Discontinuous phase Intrusion Volume (mlfc) Bukdens8y(gfrnl) Dissolution time at20*C(minutes)
0 1238 0.071 2.33
40 16.30 0.056 1.80

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For comparison the SCMC as suppBed by the manufacturer had a dissolution time of about 31 minutes at 20'C and the SCMC obtained by freeze drying a 3% aqueous solution of the SCMC had a dissolution time of about 13 mtoutes at 20'C. The formation 5 of the porous powders therefore enables the SCMC to be dissolved in an aqueous medium much more rapidly than is seen with the untreated polymer.
Example 4
10 AnexperimerrtwasccfldK^hordertoprodira
powder contaWng a hydrophlic dye to which he polymeric material is polyvinyl alcohol This powder was prepared by freezing an atomised o8-in-water emulsim h Bo^ nibogen. The emulsion comprised an aqueous continuous phase containing polyvinyl alcohol and the dye and a cfccontriuous phase comprisfrg cycbhexana Sce
15 surfactant
Example 4a
A 5% aqueous solution of porywhyl alcohol was prepared by addhg pofyvhyl alcohol (FVA ex
20 A)rtk*i,M»=90rjo-10(X»,80%hyaro
stirred wilh a type RW11 Basic IKA paddte stirrer, and hSereddyefp.0004g)andSDS(D.1g-98%, ex Aldrtch) were added followed by cyctohexane (2ml) to form an emulsion having 50% vN of discontinuous phase. The emulsion was sprayed iitofo^idnirjogenfrcfn an airbrush. The frozen emulsion was placed to a freeze-drfer overnight The powo^ contained arourti 49.9% wAvpdymer,
25 49.9% wAv surfactant and around 02% v*w dya The Wrusion volume was determined as 14.18rr%
When tie powder was exposed to an aqueous medum tie rxa%der dispersed o^ickly and tfie dye was unirbrmly Dispersed Ihrough the resulfihg solution. 30
Example 4b
A 5% aqueous solution of polyvinyl alcohol was prepared by addhg poryvftiyl alcohol (FVA ex
AWrich,M* = 9000-1W)00,8r^^ to detonised water. A sample of the solution (2ml) was
35 stirred with a type RW11 Basic IKA paddte stirrer, and direct yellow 50 (0.01g) and SDS (0.1g -
98%, ex AJdrich) were added followed by {^doriexare(6rnl)toformanerrxjlsionhavr)g75%vA/of

WO 2005/075547 PCT/EP2004/014777
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discontinuous phase. The emulsion was sprayed into iquid nitrogen from a trigger spray. The frozen emulsion was placed h a freeze-drier overnight The powder contained around 47.5% wAv polymer, around 47.5% wAv surfactentand around 5% wAvofthedye.
5 The dissolution time for The resulting powder (100mg h 2ml water stirred at 250 rpm) was 45
seconds at 20°C. For comparison toe pdyvirryl alcohol as suppled trcm toe rrmifadurer had a
dfesc*jtic*i time c^ about 23 mhutesarxl the sold d^ aqueous solution
oftteporywylatotolnadaclss^ The fctmaticn of the porous rxwders
therefore enables toe rxtyvfrrylaJo^ 10 than Is seen with the untreated poryrner. The dye was urtfbrmry dfepersed through The resulting solution.
Example 5
15 An experiment was rondix^nwde^
powder containing a hydrophobic material h which toe polymeric material is polyvinyl alcohol This powder was prepared by freezing an atomised oi4rHrateremulsiC)n'n Iquid nSrogea The ermi comprised an aqueous continuous phase containing polyvinyl alcohol and a discontinuous phase comprising a solution of the hydrophobic material in cydohexane which comprises the
20 discontinuous phase of tie emulsion. Scdwmctodecylsubhate(SDS)was used as the surfactant
Example 5a
A 5% aqueous solution of poryviryl alcohol was prepared by addhg polyvinyl alcohol (FVA ex 25 AJdrich,^=9000^1(XX)O,80%hydrolysed) todebnisedwater. Asamptec#theso)uffonC2rn0was stirred with a type RW11 Basic IKA paddte stirrer and SDSfp.lg-98%, ex Aldrtch) were added followed by a sototion of ol red dye (D.0004g) h cycJohexane (2ml) to form an emulsion having 50%vAirofc8scc«ttouousphase. The emulsion was sprayed into liquid nitrogen from an airbrush. The frozen emulsion was placed in a freeze^lrier overnight The powder contained around 49.9% 30 wAv polymer, 49.9% wAv surfactant and around 02% wAvdye.
The dissolution time for toe resulting powder (100mg h 2ml water stirred at 250 rpm) was 16 seconds at 20oC. For comparison the polyvhyl alcohol as supplied from the manufacturer had a dissolution time of about 23 minutes and the soJJd obtained by freeze drying a 3% aqueous solution 35 of the polyvinyl afcchol had a olssolutkxi time of 12 imxjtes. Tine foTrattoncf tine porous
therefore enables the polyvinyl alcohol to be dissolved in an aqueous medium much more rapidly

WO 2005/075547 PCT/EP2004/014777
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than is seen with The untreated polymer and for t» hy*DpfxDbfcoVe to be cfepersedrthe aqueous medura The dye was uniformly dfepersed twough the resuttiig soluftn Tr« o^e is not soWfe h water it cannot be dissolved or dispersed r» aqueous med^ fit has rxrt been incorporated into the powder of the present invention without using specific processing condWons krxAm to tfwse skied 5 h the art such as Wgh shear mMhg and irtasorfcteatrnent
Example 5b
A 2.5% aqueous solution of poryvhyl ata^ was prepared by acfdingrjoryvintf 10 AldrJch.Mvr=9000-10000,80% hydrorysed) to
sBrred with a type RW11 Basic IKA paddle stirrer and SDS (0.12g - 96%, ex Aldrfch) were added
fotowedby a1%scJu#nnoftriyosan^
v/v of discc>r)tir)uous phase. The emulsion was sprayed into Ir^nilrogen from a trigger sr^y. The
fra^ emulsion was placed in a firee^ 15 rxfyrr)er,about63%wAvcfsurJactart
The dissolulion time for tie resulting powder (lOOrng in 2ml water stirred at 250 rpm) was 25 seconds at 20°a For comparison the polyvinyl alcohol as suppled from the manufecturer had a dissolution time ofabout 23 minutes and the sold obtained by freeze drying a 3% aqueous soJufon 20 oftr^pofyvnylalcorKMhadacissolufiontrneof 12mtoutes. The formation of the porous powders therefore enables tie poryvhyl alcohol to be dfesoived in an aqueous medtom much more rapidly than is seen wit) the untreated polymer.
25
Example 5c
A 25% aqueous solution of polyvinyl alcohol was prepared by adding polyvinyl alcohol (FVA ex
Aldrich,M„=9000-irX>rX),80%h^ AsarrpteofitesoMfon^mQwas
30 starred with a type RW11 Basic IKA paddle stirrer and SDS (D.12g-98%, ex AWrich) were added foflowed by a 1 % solution of the fluorescer 2,5^2-benzDxazctyr)thiophene (sold under The trade name TnopalSOP) in dtailoromethane (2ml)tofonm an emulsion having 50% v/vof discontinuous phase. The emulsion was sprayed into Bqukt nitrogen from a trigger spray. The frozen emulsion was placed in a freeze-drier overnight
35
The dissolution time for the resulting powder. The powder contained about 26 % wtor of polymer, about 63% w/W of surfactant and about 11%wAv of the fluorescer. The dissolution time for the

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resulting powder (100mg ih2ml water stirred at 250 rpm)vt^ 25 secorxte at 20°C. For comparison The polyvinyl alcohol as suppled from The marwfedurerhadacfcsoWfcnfimeofaboiit and the sold obtained by freeze drying a 3% aqueous solution of the polyvinyl alcohol had a dfesobticntjmetf^mtoutes. The formation of tie porous powo^toerefore enables ttepotyvtoyl 5 afcohol to be cfcsofved to an aqueous medtom nfwchrrxrorapiotytjanisseenwjtitte
polymer. No parBctes of the fluorescer couW be observed h tie soliiBOTshovvhgtiat It had been unfonrorydfepersed.
10 Example 6
An experiment was conducted in order to produce a highly porous, rapidly dfesoMhg water-sotobte
moulded body h which the polymeric material is poly^^ alcor»L The body contehs about 44%
wAv of polyrneric material andabcut 56% wto of surfactant This body was prepared by freeang an
15 oWn-water emulsion in IqukJ nHrogen. The emulsion comprised an aqueous continuous phase
corfeiitog polyvinylalcohol and a disconttrxiousDriase comprise ScxJumdodecyl
sulphate (SDS) was used as the surfactant
A10% aqueous solution of polyvinyl afcohol was prepared by aolcSng polyvinyl alcohol (PVA ex
20 Attfcn, M»=9000-10000,80%hydrotysed) todeicxiisedwater. Asamptec*t)esolufionpnOwas
sttred with a type RW11 Basic IKA paddle stirer, and SDS(0.75g-93%,exAJdrfch)wasadded
followed Dyt7ydohexane(18nri0 to fomi an e^ The
emulsion was placed in a beaker which was placed to a thermostatic vessel containing Squid nitrogen. The frozen beaker was placed to a fireeze^Her overnight 25
In a similar manner to that described above porous bodtes were prepared from emulsions having 10%, 20%, 40% and 60% vAr of dfecontinuous phase. The emulsions from which fiese bodies were prepared using FVA (5 wt% solution) and SDS (0.05 gyrnlPVAsoMion)andtoeappropiiate volume of cyctohexane. The intrusion volume arxl tie rxilko^nsity were measured using mercury 30 porosimetry as described above. ThedJssoMScnliinieforthebcxJfes(100r^ 250rpm) are given in Table 4.
35

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PCT/EP2004/014777

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Table 4

% Discontinuous phase Intrusion Volume (mlk) Bufc density (g/rnl) Dissolution tine at20eC(rnhutes)
0 6.38 0.13 1.0
10 6.10 0.13 1.1
20 7.13 0.089 0.68
40 9.26 0.092 0.58
60 10.69 0.084 0.63
76 21.86 0.032 0.33
For comparison the polyvinyl alcohol as suppled by Vie manufacturer had a dJssoJufcn time of 5 about 23 minutes and the sold obtahed by freeze dryhg a 3% aqueous solution cf the poiyvhyi alcc]hc)lhadao1ssolii6ontiTiecfaboU12rnT)utes. The formation of tie porous bodies therefore enables the polyvinyl alcohol to be dissolved h an aqueous medium much more rapWJy than is seen wBh the untreated polyrner.
10 Bcample7
In a simfer manner to that described h example 6, porous bodies were prepared from emulsions haviig 75% rJsconliiuous phase but usiig nonoxynd 40 (sold under tie trade name IgepaJ CO-890) as file surfactant The amounts of nonoxynol 40 used are given below h Table 5. The 15 o&seilutiixi time for tfiefxdes (100^
Table 5

Amount of nonoxynol40(g/mlofFVAsolution Dissolution ftne at20'C(minutes)
0.0043 126
0.016 7.68
0.043 5.13
0.107 3.4

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For comparison toe poJyvtoyl alcohol as supplied by tie manufacturer had a dissolution time of
about 23 minutes and the soW obtained by freeze drying a 3% aqueous solution of the potyvnyl
ateorx)lhadacfcsctutSon1Jmetfabout^ The formation of fie porous bodes therefore
5 enables the polyvinyl alcohol to be dissolved in an aqueous medium much more rapiaTy than fe seen with the untreated polymer.
Ecampte8
10
An experiment was conducted in order to produce a highly porous, rapioTy ctssoMng water-soluble moulded body to which the polymeric material is sodium cartoxymethyteelulose (SCMC). The bodes contaiiabout 37.5% polymeric materiajarxlarxiut 623 %wAv of surfactant Thisbodywas prepared by freezing an caMn-water emulsion in kjuid nitrogen. The emulsion comprised an
15 ao^ieousrcintirKious prose containing s^
comprisiTg cydohexana Sodium dodecylsu^Dhate(SDS) was used as tie surfactant
A 3% aqueous soJution of S(^^ was prepared by aoy^SCMC(SCMC ex AJdrich,Mi,=90000) to dejonised water. A sample of tie soMfon (6mQ was stirred with a type RW11 Basic KA paddle 20 stirrer, and SDS(0.3g-98%,exAlciricfi)wasaoyedfolow^
emulsion having 75% v/v of cfisconfihuous phase The emulsion was placed to a beaker which was placed in a thermostatic vessel containing fquid nitrogen. The frozen beaker was placed ii a fireez&drier overnight
25 to a sirdar mariner to tiato^scittedabo^porcusbcdesw
20%,40^and60%\»VofcSsccfifihiJouspriase. The emulsions were prepared ushg SCMC (3 wt% solufon of SCMC of MW 90000) and SDS (0.05 g/rri SCMC solition) and the appropriate volume of cyctonexarie.
30 The intrusion volume and toe bulkdensity were measured using nr^rarrypcnTisirnetry as desalbed above. The dssolutjon time for the bodies (100mg in 25ml water at 8'C or 100mg in 2ml water at 20"C sttred at 250rpm) are given ii Table 6.

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Table 6

% Discontinuous phase Intrusion Volume Bulc density 0 7.76 0.106 10.13 2.47
20 10.54 0.0845 4.65 1.58
40 ia35 0.0665 3.38 0.8
60 m63 0.0389 Z82 0.42
75 29.67 0.0308 2.42 0.32
For comparison the SCMC as suppled by the manufacturer had a dfesolutJon time of about 31 5 rnirxjtesat20'Carx) the SCMC obta«r>edty
a dfcsoJution time of about 12 minutes at 8'C and about 13 minutes at 20*C. The formation of the moulded bootes therefore enables he SCMC to be dfesorved ft an aqjecius niedum mutfi nrore rapidly than is seen with the untreated polymer.
10
Example9
Inasirnferrnarr^totbatofescrtheri
SCMC were prepared from emulsions having 75% dfecontinuous phase but using dBterent 15 amounts of SDS as the surfactant The amounts of SDS used are given below ii Table 7. The dissolution time for the bodies (100mg ii 2ml water sfired at 25()rpm) are grvenh Table 7.
Table 7

Amount of SDS (jg/rnl of SCMC solution Dissolution time at20'C(minutes)
0.0079 7.12
0.0182 5.12
0.039 5.13
0.10 1.8

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Example 10
Jn a srnter manner io fliat described ii example 8, p«ousboo1es«whki)lhe polymeric matery Is SCMC were prepared from emulsions having 75% dfecontinuous phase but using nonoxyno) 40 5 (sold under tie fcade name Igepal CO890) as he surfactant TheamaurfcofnoroKynol40used are gfven below h Table 3C The dissolution tine for the bocfes (1 OOmg h 2ml water stirred at 250rpm) are given "n Table 8.
Table 8 10

Amount of nonoxynol40(gfor)lofPVAsolution Dissolution time at20*C(minutes)
0.0029 20.1
0.009 las
0.0356 11.42
0.0444 14.48
Example 11
An experiment was conducted in order to produce a Mghryporci)s,rapjdrydfesol^ water-soluble 15 moulded body h which the polymeric material is poryethytenegrycoJ (PEGX The body contains
about66.7%wAvofpoiymericmaterialandab^ Thfe body was prepared by
freezjrganoM>v>Qterernulsicnh
phase contaWhg PEG and a oTsconfinuous phase comprising cyctohexana Sodum dodecyl
sufchate(SDS) was used as tfie surfactant 20
A10% aqueous solution ofPEG was prepared by acWhgPEG(PEG exAWrich,Mw = 10000) to
deSonised water. A sample of the solution (2ml) was sfirredwith a type RW11 Basic IKA paddle
stirrer, and SDS (0.1g - 98%, ex Aktrich) was added followed by cyctohexane (6ml) to form an
emulsion having 75% v/v of discontinuous phase. The emulsion was placed in a beaker which 2 5 was placed in a thermostatic vessel contahng Iquid nRrogen. The firazen beaker was placed h a
freeze-drier overnight

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In a sinter manner to fiat described above porous bodies were prepared from emulsions having 10% and 20% VAA of dfecorthuous phase. The emulsions were prepared ushg PEG (10wt% sofcjrjon of PEG of MW10000) and SDS p.05 gfrrt PEG sokifon) arKl The appropriate volume of cyclohexana 5
TheJntnJSfonvo»jrr)earHlftebulc.d
abova The dfesoMfon time for the bodies (100mg in 2ml water stirred at 250rpm) are given h
Tabtea
10
Table 9

% Discontinuous phase Intrusion Volume (mMg) Bulk density Dissolution time at20eC(minutes)
0 526 0.12 0.33
10 5.67 0.14 0.40
20 6.51 0.13 0.42
75 17.31 0.04 0.35
15 Example 12
An exoerirriert was cc>r)ducted hordes
moulded polymeric in which the polymeric material is dextran. The body contains about 50%
polymeric material andabout 50% of surfactant This bodywas prepared by freezing an oWn-water
20 emulsion h fcpd nitrogen. The emulsion comprised an aqueous continuous phase containing
dexJranarxJaoTscontihiiousphaseoomDrisir^ Scdiumdodecylsufohate(SDS)was
used as the surfactant
A 5% aqueous solution of dextran was prepared by adding dextran (ex Ruka MW = 11000) to
25 deionised water. A sample of toe solution (2ml) was stined with a type R/V11 Basic IKApaddte
stirrer, and SDS (0.1g - 98%, ex Aldrich) was added foBowed by cyclohexane (6ml) to form an
emulsion having 75% v/v of discontinuous phase The emulsion was placed in a beaker which

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was placed h a thermostatic vessel containing Iquid nfeegen. Once frozen, the beaker was placed in a freeze-drier overnight
In a similar manner to that described above porous bcxlies were prepared fron enruls^ 5 10%and20%vAAcfcSsoonfihuousphasa The emulsions were prepared using dexiran (5wt% solution of dexiran ofMW 11000)andSDS (0.05 g/ml SCM^sc*j6cfl)arKif)eapproDriatevoIurne ofcydohexana
The htrusfon voJume and tfie bufc density were measured using mercury prjrosimety 10 abova The Dissolution time for thebodies (10t)mg h 2ml water stirred at 250^) are grven h Table 10.
Table 10

% Discontinuous phase Intrusion Volume (mlfc) Bulk density Dissolution time at20°C(minutes)
0 7.06 0.093 1.15
10 7.67 0.088 0.75
20 7.70 0.11 0.65
75 24.38 0.03 025
For comparison dexiran obtained by freeze drying a 5% aqueous solution of the dextran had a dissolution time of about 1.43 minutes
20
Example 13
An experiment was conducted « order to produce a hignlyrx)rous,raridryc!ssoI^ water-soluble moulded bodyin which the porymeric material is rx>lyvirivlalcc^whjcftcanbeusedtoc5sp«rsea 25 hydrophafc dye into water. The body contaiis about 28% wv/ porymeric material, about 69% wAv surfactant and about 3% wAv dye. This body was prepared by freezing an oB-in-water emulsion m Squid nitrogen. The emulsion comprised an aqueous continuous phase contaMhg polyvinyl alcohol and the dye and a Discontinuous phase comprising cydohexane. Sodium dodecyl sulphate (SDS) was used as the surfactant

WO 2005/075547 PCT/EP2004/M4777
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A 5% aqueous solution of polyvinyl alcohol was prepared by adding poryvhyl alcohol (FVA ex
Aldrich,M» = 90rjCMO(XX),80%rry^^ A sample ofthe solution (2ml) was
stirred v/ith a tyrxsFWII Basic KApa 98%, ex Aldrfch) was added fblowed by cyclohaxane(6m0toformanernulsto^ 5 discontinuous phase. The emufejon was placed h a beaker which was placed ha thermostatic vessel containing So^idnrtrcgea
The dissolution time for the resulfing moukfedrx>cy(100rngii2rrtwa^ The dye was unformry dispersed thrctif^f>e resulting solution. 10
Example 14
An experiment was conducted in order to produce a bighJy porous, rapidtydrssoNmg water-soluble moulded porous body ii which the polymeric material is polyvinyl alcohol which can be used to 15 disperse a hydrophobic material into water. This body was prepared by freezing an oMvwater emulsion h liquid nitrogen. The emulsion cornprfsed an aqueous continuous phase containing poryviiyj alcohol and a cfisconfiouous phase comprising a scJutjco of the Inyc^^ cyclohexana Sodium dodecylsu^hate^DS) was used as f>e surfactant
20 Example 14a
A 5% aqueous solution of poryvhyl alcohol was rxepared by addiig rx)ry\^ alcor»l (FVA ex A/dridi,Mw=9(XX)-10000,80%hycirc>/yse(/) to defonised water. AsamrpieofthescirrJm(4rn0was stirred vvilh a type RW11 Basic IKApadcJe stirrer, and SDS (0.6g - 98%, ex AkJrich) was added
25 fblowed by a solution of Fat ired 7B dye (0.01g) h cvctohexane (12n^
75% v/V of cfisconfihuous phasa The ernufsion was placed h a beaker which was placed ii a thermostatic vessel containing IqiAJ nilrogea The frozen beaker was placed ii a freeze-drier overnight The resulting moulded body contains about 28% wAv polymeric material, about 70% wAv surfactant and about 2% wAv dye.
30
The dissolution time for the resulting rrxxrloBd body (100nr^ in 2ml water) was 10 seconds at 20°C. The dye was uniformly dispersed through tie resulting solution irnparting a red coloration to the solution. When attempts were made to disperse the dye in water, particles of dye remained at the bottom of the vessel and the water did not attain any red coloration.

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For comparison the poryvirryl alcohol as suppled by fie manufacturer had a dissolution time of about 23 minutes and the sofid obtained by freeze oVy^a3%aqueaissdutJonoffl^pcJyvfiyl aJcohcthadaolssolutJctf txnetfaoctf 12mi^^ Theformafonoftbeporousbooles therefore enables the polyvinyl alcohol to be dfesdved n an aqueous iriedtonrmuch more rapjdry than is 5 seen with tJieurrlreated polymer and fe(Jlales1hedfepersfonofthedya
Example 14b
10
A 5% aqueous solution of polyvhyl alcohol was prepared by adding polyvinyl alcohol (FVA ex Attict»,M*=9000-100(X),80%hyc^^ to deforced water. A sample ofthesolutjon (4ml) was stirred with a type RW11 Basic BCA paddte sftrer, and SDS(04g-96%,exAldrich)wasadded fcflowed by a solution cf oil blue aVet^^^
15 75% vAf of dfecontinuous phase. The emulsion was placed h a beaker which was placed in a tnermostatic vessel contahtog Iquid nirogea Once frozen, the beakerwas placed ii a freeze-drier overnight The resulting moulded body contahed about 33.3% Ww poryrneric material, about 66.5% w/w surfactant and about 02% wAvdya
20 Whenthebody was exposed to an aqueous medium, the clye was uriformlyclsperBed trough fie
resulting solution irnparttog a bte When attempts were made to disperse
the dye in water, panicles of dye rematoed at the bottom of the vessel and the water old not attah any blue coloration.
25 Example 14c
A 5% aqueous solutjbn of pofyvinyl alcohol was prepared by addtog pofyvhyl alcohol (FVA ex
AttTch,M*=9000v|00(X>,80%h^ to deonised water. AsampfecfthescWton(6m0was
stirred with a type RW11 Basic IKA padie sfirrer, and SDS(0.75g-9B%,exAldrich)wasadded 30 fc*M^byasolufimcf6-Ni3hthalmiooper^
form an emulsion having 75% ViVcfolsoontfxxxe phase. The emulsion was placed h a beaker which was placed in a thermostatic vessel contaWng Iquid nitrogen. The frozen beaker was placed in a freeze-drier overnight The resulting moulded body contains about 26% w/w polymeric material, about 65% w/W surfactant and about 9% PAP.

WO 2005/075547 PCT/EP2004/014777
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It has been found that when t)e body prepared as above fe dfesoted ft water and the solution fe appied to febric dyed with a dye, for example imidfel green, the bleaching eflfect is sttl seen but the local spot damage that is caused by the presence of brger particles of t>ebJea 5 Example 14d
A 25% aqueous solution of pcfyvinyteJcohol was prepared by addtog po^viiyblcohol (PVA ex
Aldrfch, MM = 9000-10000,80% rrydrdysed) to defenised wato
was stirred wift a type RW11 Basic IKA paddte sttrer, andSDS (0.75g -98%, ex A)dtich)was
10
addedfoBowedDyasoWicHioftridosa^
50% v/V of discontinuous phasa The emulsion was placed in a beaker which was placed rt a
thermostatic vessel containing liquid nitrogen. The frozen beaker was placed ii a freeze-drier
overnight The resuihg moulded body contahs about 26% v»^ polymeric material, about 65% wAv
surfactant and about 9% tridosaa
15
The disscJutjon fin^ fbf tf»e resultiig mc 20
For comparison tie polyvinyl alcohol as suppfied by tie marxfedurer f^ a cfissc Example 14e
25 A 25% aqueous solution of polyvirrybJcohol was prepared by adding poryvhytafcohoJ (PVA ex
Aldrfch, Mw = 9000-10000, 80% hyckolysecO to ofeionised water. A sampte c^
wassfirredwilhatypeF!VV11 Basic B added folowedty a solution c#25*rs(2-benzo^ (0.12g- a fluorescer sold under
the trade name Tbopal SOP) in cfichtoromethane (12ml) to form an emulsion having 50% v/v of
3 0 discontinuous phasa The emulsion was pbced in a beaker which was placed h a thermostatic vessel containing liquid nitrogen. The frozen beaker was placed in a freeze-drier overnight The resulting moulded body contains about 26% wAv polymeric material, about 65% wAv surfactant and about 9% of he fluorescer The dissolution time for fte resulting moulded body (lOOmg «i 2 ml water) was 30 seconds at 20°C. For comparison the polyvinyl alcohol as supplied by the
35 nianufack)rerlTadadfesc*jtJmtjnTeofab^

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3% aqueous solution of toe pofyvtoyf alcohol had a dissolution tine of about 12 minutes. The formation of the porous bodies therefore enables the polyvinyl alcohol to be dfesolved in an aqueous medtom much more rapiofy fen is seen with the untreated polymer and fedtates tf)e dispersion of the hydrophobic material. 5
Example 14f
A5%aqtjeousso)utimofpofyvtoylafcooolwaspr^^ ex
AWrfch,^=900f>1O)M,8c)n(4nrt)was
10 sttredwitha^pel^11BasfelKAp9do1esttrer,arxl SDS(0.3g-96%, ex Aldrich) was added
followed bya 10%solution of poJystyreiTe(alTydrophobfcpor
emulsion having 60% v/vof discontinuous phase. The emulsion was placed to a beakerwhfch
was placed to a toenrostalfc vessel oonlatotoglr^
freeze-drieroverright Theresulltogrrwuldedrxxjycontatosab^ 15 about27%w/wsurfedantandaboirt55%wAvDorystyrene.Tr)ed
rnou)o^bc)dy(100rrgto2mlwater)was15secor)dsat200C. TheFSwasmSormlycfispersedas
a latex to the dispersion of toe FVA.
Example 14g 20
A 5% aqueous solution of polyvtoyj alcohol was prepared by adotogpolyvhyl alcohol (PVA ex Aldrich, M*=9000-10000,80% hydrorysed) to defonised water. Asampte of toesoMfon (5ml) was sftredwithatyperWilBasfcJKApaG^sttoer.and SDS(0.3g-96%,exAWrfch)wasadded followed bya 9.45% solution of pdy(rX-tectideK»gryco^
25 porymer)toQdof)exane(5m0toformane^
emulsion was placed to a beaker which was placed to a thermostatic vessel contetotog Squid nitrogen. The frozen beakerwas placed to a freeze-drter overnight The resulting moulded body contatos about 25% wAv polymeric material, about29%wAvsurfeclant and about 46% wAv hydrophobic polymer. The dissolution time for the resulting moulded body (100mg to 2ml water)
30 was2mtoutesat20cC.TbeRGwasuniforrniycl^
Example 14h
A 1.67% aqueous solution of polyvinyl alcohol was prepared by adding poryvinyl alcohol (FVA ex 3 5 Aldrich, M» = 9000-10000,80% hydrorysed) to defonised water. A sample of the solution (6ml) was

WO 2005/075547 PCT/EP2004/014777
- 29 -
stin^vwlhatypeRVV11Ba^D MW140000 ex Aldrich) to toluene (6ml) 1o form an emulsfonhav»Tg50%vA^cfdJscortir)Uous phase. Theernutefonwaspfecediia beakerwhfchwasplacedhathermostaticvesselcontaMng 5 lquJdnarogen.7Iie frozen beaker was placed to a freeze^Her overnight The result
body contatos about 39% wAv porymerfc material, about 49% wAv surfactant arxi about 12% wAv hydrophobic polymer. The dfesotoBon trie for the resulting mouk^ was3mtoutesat20°C.Therryotophri)fccopo^ dfepersfonoftoePVA 10
Example 15
An experiment was conducted h order to produre highly porous, rariJydfes^ porous bodtes to which the polymeric material is SCMCwhichcanbeusedtodfepersea 15 hydrophobic polymeric maferial toto water. These bc 20 A 3.3% aqueous solution ofSCMC was prepared by addtogSCMC to ozonised water. A sample
of the sototion(6mQ was stirred wfr a t^ SDS(0.25g-98%,
exAldrict))wasaddedfc4cwedbyasc4uitonofpc^ (0.06g MW 350000 ex
Aldrich) in toluene (6m0 to form an emulsion ha\^ 50% vArtftisconttouous phase
25 Example 15a
The above emulsion was sprayed toto Squid nilrog^ from an airbrush The ftozene
placed hafreeze^Jrieroverr^ttogrVepcirousb^
for the resulting powder (100mg in 2ml water) was 1 minute at ^"C
30
Example 15b
The above emulsion was placed in a beaker which was placed in Iquid nitrogen to freeze the emulsion The frozen emulsion to toe beakerwas placed in a freeze ciriero\/emight to give a porous

WO 2005/075547 PCT/EP2004/014777
- 30 -
moulded body shaped as the inside of the beater. The d»ssc>lutjmtirr)e for toe resuKtog moulded body (1 OOrng to 2ml water) was 40 seconds at 20*C
Example 15c 5
A beaker was placed to a thermostatic vessel and Iquid nRncgen was placed iibotfi fie teaker and the vessel. The emulsion prepared above was acideddropw^firomarieedtetotteiquidriitrogen hthebeaker using a A-99FZRazel syringe pump. The beaker was placed to afreet drier overnight to give spherical beads. The cfesdu&n tire for f)e result 10 was1.2rr*xrtesat20,,C
Example 16
An experiment was conducted to oro^ to prod^
15 porous bodies to which toe polymeric material is SCMCwhichcanbeusedtodfepersea
hydrophobic polymeric material and a hydrcphcbk;a(^ve material totowator. These bo
prepared by freeztog oi-to^vater emulsion to io^nrlrcgea The emulsion coriprised an a
continuous phase contatotog SCMCarrf a dfeccoltouxjspriase comprising a scto
hydrcphc>c*polyrnerarKJ1hehyd^ Scd«ndodecylsutoharte(SDS)
20 wasusedastoesurfeciant
A 3.3% aqueous solution of SCMC was prepared by addtogSCMC to deionfeed water. Asample
of the sc*ifoi(^v^ stirred w»i a type SDS(0.25g-98%,
exAfcWch)wasaddedfbltowedbyasoMtonofp^ (PMMA0.06g MW
25 350000 ex AWfch)ar)d2,54)isC24)era^^
trade name TtoopaJ SOP) to toluene (6mJ)tofonm an emulskxihavtog50^v^rfdfecon*)uous phase
Exampfe16a 30
The above emulsion was sprayed rito liquid nitrogen fromanairbriish.Theirczenermifeionwas placed in a treeze-drier overnight to give porous bodies to the form of a powder. The dissolution time for the resulting powder (100mg to 2ml water) was 30 seconds at 20"C

WO 2005/075547 PCT/EP2004/014777
- 31 -
Example 16b
The above emulsion was placed h a beakerwhfch was placed hftqukJnarogen to freeze The emulsion. The frozen emulsion ii tie beakerwas placed ha freeze drier overnight to give a porous 5 nx>ulded body shaped as tie frside of the beaker body (100mg ii 2ml water) was 30 seconds at20,,C
Example 16c
10 A beaker was placed in a thermostatic vessel and i^^iTSrogen was placed hbo^ the beaker and thevesseL Theemukfon prepared above was added dropwisetromaneecletotieB^idnarogen in tie beaker using a A-99F2Razel syringe pump. The beakerwas placed in a freeze drier overnight to give spherical beads. The dssoJufJon tirte for tie resurrhgbeao^(100mg)ri2rrrf wafer) was 1 minute at 20'C
15
Example 17
Ane*penmer)tvvascorxJuctedinc«j^ porous bodies hwhtrii the polymeric materte^ 20 [PDMAEMA). These bcrfes were prepared by f^^
The emulsion comprised an aqueous ccfvrhiKxrs phase containing PDMAEMAanda drscontjhuous phase compnsiig cydohexana Socfiumcicdecyl sulphate (SDS) was used as tie surfactant
25 2-(p»r)ethylarnho)ethytnrietiacry^
O.61rmx>0 were dfesotved h dtytetrahydrciu^
reiTK>ved by buob&ig nitiDgen thrcugh tte
to60 "Cundera nitrogen atmosphere for 24 hours arid tiencooted to room temparature,
concentrated fri vacuo and the residue was dripped iitoccW petroleum et)er(4&^^ fraction) h 30 order to precipitate the polymer. The pcJymer was filtered off and dn^cwemightu^
give poly(2-N,lNkJOTiethvfamir^ as a white crystarlne powder
A 5% aqueous solution of PDMAEMA was prepared by deserving tie PDMAEMA prepared above in debnised water. A sample of the solution (8ml) was stored with a type RW11 Basic IKA paddle

WO 2005/075547 PCT/EP2004/014777
- 32 -
stirrer.and SrX(1g-98%,exA)oYkfi)wasaddedfbfcw^ emulsion having 75% vVofcSsconfihuous phase
Example 17a 5
The above emulsion was sprayed Wo BqukJ nbogen from an aforush. The frozen placed to a freeze-drier overnight to give porous bc Bcample17b 10
The above emulsion was placed ii a beaker which was placed in liquid nitrogen to freeze Hie emulsion. The frozen emufeion h the beakerwas placed In a freeze drier overnight to give a porous moulded body shaped as the hskte of the beaker.
15 Example 17c
A beakerwas placed h a thermostatic vessel and iquid niircgen was placed h both tie beaker and the vessel. The emulsion prepared above was added dfrcipwisefrcmarieetletotieBquidrtfrogen in tie beaker using a A-99FZ Raze! syringe pump. The beaker was placed ha freeze drier 20 overnight to give spherical beads
PDMAEMA is irisolubte to water at high temperate
drops. The porous bodes prepared above are therefore able to remain Wact at higher temperatures but wicfssofve or cfisperseatlowertemperatures. Samples (100mg) of the products 25 ofexamples17aJ7barri17cwefesfrredwilhwate
temperature at which tie bodies dfesorved:- Example 17a 57'C, Example 17b 57* and Example 17c55'C.
Example 18
30
An experiment was conducted in order to proo\x* highly pc>rc>us,rapiclryd
porous bodies in which the polymeric material is rx>lyC2^,r>kfirnethylamir^
[PDMAEMA] which can be used to dfeperse a hydrophobic material into water. These bodies were
prepared by freezhg an oj-in-water emulsion ii Iquid nitrogen. The emulsion comprised an
35 aqueous contiguous phase containhg PDMAEMAarxi a discmtirurous phase comr^

WO 2005/075547 PCT7EP2004/014777
33 -
solufion cf the hydrophobic material ft cydohexane. Socium dodecyl sulphate (SDS) was used as the surfactant
A 5% aqueous solution of PDMAEMA was prepared by dfesoMhgftePDMAEMA prepared h 5 Examrie17arx>vehcteicr»sedwaten^
Bask;KApaddJestirrer,and SDS(1g-96%,exAttich)v^addedfbllowedbyaso^ solvent green 3 dye (O.Q2g) in cyctorexane(24m0toformanenw»r5^ drscorjtjnuous phase
10 Example 18a
The above emulsion was sprayed hto Squid parogen fromanairt)rusruTr^lTDzenemulsfonwas placed in a freeze-drier overnight to gfve porous bodies in the form of a powder.
15 Example 18b
The above emulsion was placed fri a beaker which was placed ft liquid nirogen to freeze the emulsion. The frozen emulsion ft the beaker was placed ha freeze drier overnight to give a porous moulded body shaped as the inside of the beaker.
20
Example 18c
A beaker was placed in a thermostatic vessel and IquidnBrr^en was placed h both f»e beaker and the vessel. The emulsion prepared above was ado^dropwisefromaneedtetotJielquidrtrjDgen 25 htherjeakeriishgaA^FZRazelsyriigepurrix Therjeakerwastfaoadftafireezedrier overnight to give spherical beads.
PDMAEMA is JnsoJubte in water at high temperatures but tecomes soluble as th^ drops. The porous bodies prepared above are t)erefbre able to reman intact at higher 30 temperatures but will dissolve or disperse at lower temperatures. Samples (100mg) of the products of examples 18a, 18b and 18c were stirred with water at 65'Carxl the solution allowed to cooL The temperature at which tte bodies dfesolved and Hie dye was released were:- Example 18a 58"C, Example 18b 57'C and Example 18c 52'C.

WO 2005/075547 PCT/EP2004/014777
- 34 -
Example 19
An experiment was concluded n orderto produce highly porous, rapHydfeso^^ porc*Jsbc emulsion comprised an aqueous contftjous phase ccirtaWhg FIDEABdAarriadfecontJhuous phase oomprisiig(^cW)exana Hybrane(exDSM)wasused3sthesurfecfant
2-)ethyl methacrybte (10g, 0.054mo0^«j2^azoc*sisobirtyronib* (0.1g, 0.61rnmof) 10 were cissorvedh dry telrarrydroli^
bubbAr)g nitrogen t)roigh #)e solutim f^
unrJer a nitrogen atnxjsphere tor 24 hours and t^
vacuo and he residue was dripped hto cold aostoni^hc>ro^toprec#latelhe
polymer was filtered offand dried overnight ureter vacujm to cjivepoly£-HN-15 cSethyterninc«thyfcT)ethacrylate)PDEAEMA3sac^
A10% acidffled aqueous solution ofPDEAEMA was prepared by cfesorvhgtjeHDEAEMAh defonised water and addryhg with 2M hydrochloric ackl AsarrpIecf*)esc*jlfon(4rnQwassrJ7ed with a type RW11 Basic KApadcfesfirrer, and hyoiane(0.5gexDSM)wasaddedfolawedby 20 cydc*)exane(12mQtofbimanemulsto
Example 19a
The trigger spray airbrush. The frozen ermjteicri was fjlaced in a freeze^in^ overnight to grve 25 DorousbcKfiesinf^tbrmofapowcter.
Example 19b
The above emulsion was placed in a beaker which was placed hlk^id nitrogen to freeze the 30 emulsion. The frozen emulsion in thebeakerwas placed in a freeze chiercA^rnight to give a porous moulded body shaped as f)e frside of the beaker.
35

WO 2005/075547 PCT/EP2004/014777
- 35 -
Example 19c
A beaker was placed to a thermoslalfc vessel and iquH nHrogen was placed h both the beaker and thevesseJ. Theemufefon prepared above was added dropwise from a rieedte to toe fio^ nitrogen 5 totoet>eakerusiigaA-99FZRazelsyringepump. The beakerwas placed ba freeze drier overnight to give spherical beads.
PDEAEMAistoscdubtehwateratbfo^pHbutbea^ The porous
bodes prepared above are therefore able to remain hiadathioj)erpHbutwBdfesorVeord^)erse 10 at tower pR Samples (100mg)ofthe products rfexaniples 15a, 145 arxl 16c were sflrredvvJIhIM aqueojssocSumhyoYoxictescWxxiat20*CarKithesc^ hydrochloric acid. The pH at which toe bcxiesdissc>lvedwqasaroui^^ Example 19a, Example 19b and Example 19a
15 Example 20
The powders of Example 5c were tested to determine the depcertion of tie fluoresce, 2,5-bis(2-benzaxazctyQtoiophene, onto cotton and nybnJabria
20 Deposition cffluorescerfromlr^
blank (Sample A) was carried out where toe ctoto was washed with defonSsed water (18 ml) only, and a comparison (Sample B) was washed wih toe fluorescer(0.36mg)todeicrisedwater(18ml)i The powder (3.58 mg) was dfesolved hto deionised water (18 rrt) to give toe same amount of Fluoresceraswas contatoed w»)to toe powcler(SampteC> The wasMig was carted out tor 45
25 rntoulesh each case; toe doths were I'emos^rin^ afc
Ganz Whiteness measuremente were carried out on each sarrpteiistogaHunteriabUKrascanXE Spectrophotometer which measures the reflectance of a sample over a wavelength range of 30 360nm to 750 nm at 10nmhtervQ& Ganz Whiteness measures
calibrated UV source. Arborescent white tie of known Ganz Whiteness was used to cafibrate the UV content of toe incident fight source during measurement The Ganz Whiteness Index measures perceived whiteness along a blue-yellow axis ratoer toan neutral white, taking into account the human preference for bbefeh shades of whita The greater the value of Ganz Whiteness the whiter

WO 2005/075547 PCT/EP2004/014777
-36 -
(or more bbeish white) the nrraiery-100 u^ The results obtained are
given r> Table 11 below
Table 11

Material and rbrnnufetfon Ganz Whiteness Index
Cotton-pr&wash 8022
Cotton-SampleA 84.02
Cotton-Sample B 91.18
Cotton -SampteC 114.91
hlvton-pre-wash 75.51
Nyton-Sample A 78.53
Nylon-Sample B 86.91
Nyton-SampteC 98.36
5
The hgher Ganz Whiteness values obtained win tt» powder of tie present invent todcateftat fine fluorescerrce efficiency of tf>efluoresra used in water alone
10 Example 21
to a simtermannerto fiat described h Example 20,Thennouto^ bodies of Examplepte14e {Sample D) were tested to determine the deposrrfon ()f2,54)js(2*enzoixazcJyDttifoprienec^ nyton febria The results obtained are grven to Table 12 below 15
Table 12

Material and formulation Ganz Whiteness Index
Cotton-pre-wash 80.22
Cotton-SampleA 84.02
Cotton -SampteB 91.18
Cotton-Sample D 113.87
Nyton-pre-wash 75.51
Nyton-Sample A 78.53
Nylon-SampteB 86.91
Nyton-Sample D 90.92

WO 2005/075547 PCT/i;P2004/014777
- 37 -
The higher Ganz Whiteness values obtaned wit) The nxulded body of the present irrvention indfcate tiat the fluorescence efficiency of the fluorescer on ftefabnc is rnuch higher lhan when the fluorescer is used ii water alone
5
Example 22
Inasimtermamertotiatotescrtoe^ E)weretestedtoctetenriir»t)eo^pc€rficrtof2,^^ 10 nyton fabric. The results obtahed are given in Tabfe13bebw
Table 13

Material and formulation Ganz WhSeness Index
Cotlon-SampleA 84.56
Cotton-Sample B 84.6
Cotton-Sample E 102.61
Nyton-Sample A 78.61
Nyton-Sample B 80.14
Nyton- Sample E 106.63
The higher Ganz Whiteness values obtatoed wflh the moulded bodyofthe present hventton show 15 ttetthedepc«ilionc>ffl>efluarescerontothef^^ in water atone.
Example 23
20 TTieantintonobial effect of tieln^c^anc^
Example 14d were observed"« the fofcwing experiment
Cultures of S.epkiei7ridis and Corynebacterium A were prepared by hocubting the appropriate 25 sterile broths (Brain Heart Infusion broth, Qxoid, UK for S.ep*fe/mfcfe and Coryne broth for Coiynebacteiium A, (Tryptone soy broth (3.0%), Yeast extract (1.0%X Tween 80 (0.1%)) and incubating wifo shaking for 24 h at 37°C. Cultures were then centrifuged and resuspended ii the appropriate broths to an optical density (OD) at 600nm of 0.01 (apprcx 5.0 xlO6 CFU/ ml for S.eptiermkJis and 1.63 x 106 CFU/ ml for CorynebacbriumA).

WO 2005/075547 PCT/EP2004/014777
- 38 -
Stock solutions of The powder of Example 4c, tie moulded body of Example 14d and a 30% solution of trictosan to ethanol were prepared h both sets of broths to a final trictosan concentration of 0.04% (400ppm)L These were fMersterifeed twough 02)*M syringe liter (Whatman, UK)L These stocks were seriaJy diluted (doubBng dlutions) Into a row of weBs h 96 wel microtitre plates, by 5 acti^85plcf stock to thefts and secorriwe&T^
broth. The wel contents were txxoughly mixed by dBrpjrgarddfecliarpjng the pipette. 85fJ was then removed from the second wel Wo the third wel, containhg 85fil of broth and the process repeated until wel 10. The final 8£>nl were removed and olscarded.Wels11and12wereusedas controls and contaned 85pl of sterite broth only. Rxir rows were used per fbnnirb^
10 ideate tests. The fftst 11 weOs were kxxxHatedwHh85filcfba
mixed, 85pl of sterile broth was added to wel 12 as a negative control The OD was measured at 600nm using a plate reader spectrophotometer (Spectramax Plus mkaropbte spedrcphotometer, molecular devices, UK) before the plates were sealed and toajbatedat37^far24h.TheODwas again nieasured at 600im Grwrti nhi^^
15 control (wel 11) on the basis ofODfbr each concerrbatfon tested Tte data vvos ptotted as bkxxte concentration vs growth hhfortion and the graphs used to estimate the concentration at which he formulation caused a 50% hhfcition of growix This was defined as he rvflC for that formulatioa The results are given h Table 14
20
Table 14

Formulation MIC vs S.epkiermkJfs MICvs CoiynebacteriumA
Tridosan containing powder of Example 4c 0.05ppm 30ppm
Trictosan containing moulded body of Example 14d 0.05ppm 30ppm
Trictosan/ ethanol 0.075ppm% 43ppm
The tower MIC values seen wffli the powder and moulded body of tf>e present invention hdfcate 25 that the activity of the trictosan is imprcA^ present iiventioa

^y/U-J I'D J.V>:00 jfAA -T-4-J _'!.! 1011 OiOI.I
29-Q3-2006
EP0414777
39 CLAIMS
1. Porous bodies comprising a three dimensional open-cell lattice which porous
bodies are water dispersible or water soluble such that materials contained within the
lattice are dispersed when the porous bodies are exposed to an aqueous medium,
the porous bodies containing
(a) 10 to 95% by weight of a water soluble polymeric material and
(b) 5 to 90% by weight of a surfactant,
said porous bodies having an intrusion volume as measured by mercury porosimetry of at least 3ml/g
with the proviso that said porous bodies are not spherical beads having an average bead diameter of 0.2 to 5mm.
2. Porous bodies as claimed in claim 1 wherein ine Dodies are in the form of powders, beads or moulded bodies.
3. Porous bodies as claimed in claim 1 or claim 2 wherein the polymeric material is a natural gum, a polysaccharide, a cellulose derivative or a homopolymer or copolymer comprising (co)monomers selected fromi:-
vinyl alcohol,
acrylic acid,
methacrylic acid
acrylamide,
methacrylamide
acrylamide methylpropane sulphonates
aminoalkylacrylates
aminoalkylmethacrylates
hydroxyethylacrylate
hydroxyethylmethylacrylate
vinyl pyrrolidone
vinyl imidazole
vinyl amines
vinyl pyridine
ethyteneglycol
ethylene oxide
ethyleneimine
ved at the EPO on Mar 29. 2006 17:52:51. P« AMENDED SHEET

CiiMSJMMD- 04804363

icy
^

styrenesulphonates ethyleneglycolacrylates ethyteneglyool methacrylate
5 4) Porous bodies as claimed in daim 3 wherein the cellulose derivative is selected from xanthan gumr xytoglucarr, cellulose acetate; methylcellutose, methyethylcelluloser hydroxyethylcellulose, hydroxyethylmethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose (HPMC), hydroxypropylbutylcellulose, ethylhydroxyethylcellulose,
carboxymethylcellulose and its salts, or cartwxyrnethyl-hydroxyethylcellulose and its salts 10
5) Porous bodies as claimed in any preceding claim wherein the surfactant is non-ionic anionic,
cationic, or zwitterionic
6) Porous bodies as claimed in any preceding claim wherein the surfactant is selected from
15 ethoxylated triglycerides; fatty alcohol ethoxylates; alkylphenol ethoxylates; fatty acid ethoxylates;
fatty amide ethoxylates; fatty amine ethoxylates; sorbitan alkanoates; ethylated sorbitan alkanoates; alkyl ethoxylates; pluronics; alkyi poryglucosides; stearol ethoxylates; alkyl poryglycosides; alkylether sulfates; alkylether carboxylates; alkylbenzene sulfonates; alkylether phosphates; dialkyl sulfosucrinates; alkyl sulfonates; soaps; alkyl sulfates; alkyl carboxylates; alkyl phosphates; paraffin
20 sulfonates; secondary n-alkane sulfonates; alphaoiefin sulfonates; isethionate sulfonates; fatly amine salts; fatty diamine salts; quaternary ammonium compounds; phosphonium surfactants; sulfonium surfactants; sulfonxonium surfactants; N-alkyl derivatives of amino acids (such as glycine, betaine, aminopropionic acid); imidazoline surfactants; amine oxides; amidobetaines; and mixtures thereof
25
7) Porous bodies as darned in any preceding daim wherein the porous polymeric bodies have
water soluble or water insoluble materials incorporated into the polymeric lattice
8) Water soluble porous polymeric bodies as claimed in claim 7 wherein the water soluble material
30 is selected from water soluble vitamins; water soluble fluorescers; activated aluminium
chlorohydrate; transition metal complexes used as bleaching catalysts; water soluble polymers; diethyteretriarrtinepentaacetic acid (DTPA); primary and secondary alcohol sulphates containing greater than C8 chain length or mixtures thereof
AMENDED SHEET

$£ - 41
9) Water soluble porous polymeric bodies as dairned in daim 7 wherein the water insoluble material
is selected from antimicrobial agents; antidandruff agent; skin lightening agents; fluoresdng agents;
antifoams; hair conditioning agents; fabric conditioning agents; skin conditioning agents; dyes; UV
protecting agents; bleach or bleach precursors; antioxidants; insecticides; pesticides; herbicides;
5 perfumes or precursors thereto; flavourings or precursors thereto; pharmaceutically active materials; hydrophobic pdymeric materials-andmixturesthereof.
10) A method for preparing water dispersible or water soluble porous bodies comprising a three
dimensional open-cell lattice containing
1.0 (a) 10 to 95% by weight of a water soluble polymeric material and
(b) 5 to 90% by weight of a surfactant,
said porous bodies having an intrusion volume as measured by mercury porosimetry (as hereinafter
described) of at least 3 ml/g
with the proviso that said porous bodies are noi spnencai oeads having an average bead diameter 15 of02to5mm
comprising the steps of:
a) providing an intimate mixture of the polymeric material and the surfactant in a liquid
medium
20 b) providing a fluid freezing medium at a temperature effective for rapidly freezing the
liquid medium;
c) cooling the liquid medium with the fluid freezing meaium at a temperature below
the freezing point of the liquid medium for a period effective to rapidly freeze the
liquid medium; and
25 d) freeze-drying the frozen liquid medium toform the porous bodies by removal of the
liquid medium by sublimation.
11) A method as claimed in daim 10 wherein the cooling of the liquid medium is accomplished by
spraying an atomised emulsion into the fluid freezing medium; by dropping drops of the emulsion
30 into the fluid freezing medium or by pouring the emulsion into a mould and cooling the emulsion in the mould.
12) A method as claimed in daim 10 or 11 wherein the polymeric material is a natural gum, a
polysaccharide, a cellulose derivative or a homopolymer or copolymer comprising (co)monomers
35 selected from:-
AMENDED SHEET

«d®ttUH£2& OGtiRfe SflBS
vinyl alcohol,
acrylic acid,
methacrylicacid
acrylamide,
5 methacrylamide
acrylamide methyfpropane sulphonates
aminoalkylacrylates
aminoalkylmethacrylates
hydroxyethylacrylate
10 hydroxyethylmethylacryfate
vinyl pyrrolidone
vinyl imidazole
vinyl amines
vinyl pyridine
15 ethyleneglycol
ethylene oxide
ethyleneimine
styrenesulphonates
ethyleneglycolacrylates
20 ethytenegrycd methacrylate
13) A method as claimed in any one of claims 10 to 12 wherein the surfactant is non-ionic, anionic, cationtc, or zwitterionic
25 14) A method as claimed in any one of claims 10 to 13 wherein the surfactant has an HLB value of 8 to 18
15) A method as claimed in any one of claims 10 to 14 wherein the surfactant is selected from ethoxyiated triglycerides; fatty alcohol ethoxyiates; alkylphenol ethoxylates; fatty acid ethoxytates;
30 fatty amide ethoxylates; fatly amine ethoxylates; sorbitan alkanoates; ethylated sorbitan alkanoates; alkyl ethoxylates; pluronics; alkyl poryglucosides; stearol ethoxyiates; alkyl poryglycosides; alkylether sulfates; alkylether carboxytates; alkylbenzene sulfonates; alkylether phosphates; dialkyl sulfosuccinates; akyl sulfonates; soaps; alkyl sulfates; alkyl carboxylates; alkyl phosphates; paraffin sulfonates; secondary n-alkane sulfonates; abha-olefin sulfonates; isethtonate sulfonates; fatty
35 amine salts; fatty diamine salts; quaternary ammonium compounds; phosphonium surfactants;
AMENDED SHEET

Printed^20Al 0/2005 :QlJ^S|AJ|a WlimB

V^

^ - 43 -

sulfonium surfactants; sulfonxonium surfactants; N-alkyl derivatives of amino acids (such as glycine, betaine, aminopropionic acid); imidazoline surfactants; amine oxides; amidobetaines; and mixtures thereof
5 16) A method as claimed inclaim 10 wherein the intimate mixture is an oil-in-water emulsion
17) A method as claimed in claim 16 wherein the discontinuous phase of the emulsion.comprises 10 to 95% by volume of the emulsion
10 18) A method as claimed in claim 16 wherein the discontinuous phase of the emulsion comprises 20 to 60% by volume of the emulsion
19) A method as claimed in daim 16 wherein the discontinuous phase of the emulsion is selected
from alkanes; cydic hydrocarbons; halogenated alkanes; esters; ketones;
15 ethers; volatile cydic silicones and mixtures thereof
20) Solutions or dispersions comprising water soluble polymeric materials and surfactant formed by
exposing the porous bodies of any one of daims 1 to 9 to an aqueous medium.
20 21) Solutions or dispersions comprising water soluble polymeric materials, surfactant and a hydrophobic material formed by exposing the porous bodies of daim 7 having the hydrophobic material contained therein to an aqueous medium.
DATED 2 0 JUL 2006
UNILEVER PLC
(S. Venkatramani) Authorised Signatory

Documents:

864-mumnp-2006-cancelled pages(4-1-2008).pdf

864-mumnp-2006-claims(amended)-(4-1-2008).pdf

864-mumnp-2006-claims(granted)-(21-4-2009).pdf

864-mumnp-2006-claims.pdf

864-mumnp-2006-claims.rtf

864-mumnp-2006-correspondance-received.pdf

864-mumnp-2006-correspondence 1(8-5-2008).pdf

864-mumnp-2006-correspondence 2(10-11-2006).pdf

864-mumnp-2006-correspondence(ipo)-(8-5-2009).pdf

864-mumnp-2006-description (complete).pdf

864-mumnp-2006-description(granted)-(21-4-2009).pdf

864-mumnp-2006-form 18(10-11-2006).pdf

864-mumnp-2006-form 2(granted)-(21-4-2009).pdf

864-mumnp-2006-form 2(title page)-(20-7-2006).pdf

864-mumnp-2006-form 2(title page)-(granted)-(21-4-2009).pdf

864-mumnp-2006-form-1.pdf

864-mumnp-2006-form-2.doc

864-mumnp-2006-form-2.pdf

864-mumnp-2006-form-3.pdf

864-mumnp-2006-form-5.pdf

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Patent Number 233909
Indian Patent Application Number 864/MUMNP/2006
PG Journal Number 25/2009
Publication Date 19-Jun-2009
Grant Date 21-Apr-2009
Date of Filing 20-Jul-2006
Name of Patentee UNILEVER PLC
Applicant Address UNILEVER PLC, UNILEVER HOUSE,BLACKFRIARS, LONDON EC4P 4BQ
Inventors:
# Inventor's Name Inventor's Address
1 FOSTER Alison Jayne Unilever R&D Port Sunlight, Quarry Road East, Bebington, Wirral, Merseyside CH63 3JW,
2 COOPER Andrew lan University of Liverpool, Department of Chemistry, Senate House, Crown Street, Liverpool, L69 3BX
3 RANNARD Steven Paul Unilever R&D Port Sunlight, Quarry Road East, Bebington, Wirral, Merseyside CH63 3JW,
4 ZHANG Haifei University of Liverpool, Department of Chemistry, Senate House, Crown Street, Liverpool, L69 3BX,
PCT International Classification Number C08J9/16, 9/28
PCT International Application Number PCT/EP2004/014777
PCT International Filing date 2004-12-23
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 0401950.1 2004-01-28 U.K.