AU672598B2 - Surfactant - Google Patents

Description

ANNOUNCEMENT OF THE LATER PUBLICATION OF INTERNATIONAL SEARCH REPORT '0 SLc,13! 1 73 PCr INTERNATIONAT PPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification 5 (I1) International Publication Number: WO 93/18851 C08G 81/02, C08J 3/24, BOF 17/52 A3 (43) International Publication Date: 30 September 1993 (30.09.93) (21) International Application Number: PCT/GB93/00524 (81) Designated States: AU, CA, JP, KR, NZ, US, European patent (AT, BE, CH, DE, DK, ES, FR, GB, GR, IE, IT, (22) International Filing Date: 12 March 1993 (12.03.93) LU, MC, NL, PT, SE).

Priority data: Published 9205701.7 16 March 1992 (16.03.92) GB With inernational search report Before the expiration of the rtie limit for amending the claims and to be republihed in the event of the receipt of (71) Applicant (for all designated States except US): IMPERIAL amendments.

CHEMICAL INDUSTRIES PLC [GB/GB]; Imperial Chemical House, Millbank, London SWIP 3JF (88) Date of publication of the international search report: 2)2 October 1993 (28.10.93) (72) Inventor; and Inventor/Applicant (for US only) DOBSON. Derrick, Clifford [GB/GB]; 7 Hopwood Avenue, Heywood, Lancashire OLIO 2AX (74) Agents: DRAGGETT, Peter, Thornton et al.; ICI Group 6 Patents Services Dept., P.O. Box 6, Shire Park, Bessemer Road, Welwyn Garden City, Hertfordshire AL7 IHD

(GB).

(54) Title: SURFACTANT (57) Abstract A surfactant characterised by a plurality of addition-copolymer chains, on each chain an average of at least 0.5 chemisorptive groups and at least one monovalent polyether residue; and between the chains at least one divalent polyether residue, a method of making it, a dispersion containing the surfactant and a dispersed solid, a polymer composition that comprises the surfactant and a plasticiser, a method for making the dispersion, a dispersible solid comprising the surfactant, and a product coated with material comprising the discontinuous phase of the dispersion.

WO 93/18851 PCT/GB93/00524

SURFACTANT

This invention relates to a surfactant, a method of making it, a dispersion containing the surfactant and a dispersed solid, a polymer composition that comprises the surfactant and a plasticiser, a method for making the dispersion, a dispersible solid comprising the surfactant, and a product coated with material comprising the discontinuous phase of the dispersion.

According to a first aspect of the invention, a surfactant is characterised by a plurality of addition-copolymer chains, on each chain an average of at least 0.5 adsorptive or chemisorptive groups and at least one monovalent polyether residue; and between the chains at least one divalent polyether residue.

The terms "adsorptive" and "chemisorptive" herein indicate that the chains of the surfactant are capable of adsorption or chemisorption to the surface of a phase other than that which is or comprises the surfactant.

The balance of the relative proportions of the chains and the residue is such that the surfactant has sufficient solubility as such or as a salt in a liquid to exert surface activity, either in that liquid or on the surface of a solid to which it is applied by way of such a solution. Whereas it is believed that the surfactant is mainly a two-dimensional molecule, it may be at least partly three-dimensional, provided that it has sufficient solubi ity.

A particular embodiment of the surfactant cf the present invention is characterised by the following features: a plurality n of addition-copolymer chains; on at least n-2 chains, at least one, especially 3-10, optionally salified carboxylic acid groups and at least two carboxylic ester groups; at least one, especially 2-6 of the carboxyl ic ester groups in each chain having as its alcohol residue a monovalent polyether residue; and WO 93/18851 PCT/GB93/00524 2 at least one other of the carboxyl ic ester groups in each chain having as its alcohol residue a divalent polyether residue, a further end of which is the alcohol residue of the carboxylic ester group of another of said addition-copolymer chains; and optionally a carboxylic ester group having as its alcohol residue a monovalent hybrocarbyl residue, e.g.

hydrocarbyl.

The addition-copolymer chains may consist of carboxyl-carrying units present as acid or ester in features and (ii) other units.

The carboxyl-carrying units may be for example (meth)acrylic units, but are preferably 1,2-dicarboxylic units such as maleic units. The number of such carboxyl groups per 100 addition-copolymerised monomer residues in their overall relative proportions is preferably in the range of 25 to especially 45 to 55. The acid value of the addition-copolymer chains, assuming hydrolysis of any anhydride units is suitably in the range of 150-350, especially 250-310, mg KOH/g. The free carboxylic acid groups in each chain are optionally salified with for example a plurality of monovalent cations such as alkali metal, e.g. sodium, or ammonium ions. The other units may for example comprise ethylene, vinyl esters, vinyl ethers or acrylic esters, but are most conveniently styrene.

The average molecular weight of each of the addition-copolymer chains is suitably in the range of 1000 to 5000, especially 1500 to 300.

The monovalent polyether residue is suitably derived from an ether-terminated polyalkylene glycol. Such poiyalkylene glycol (apart from its terminating hydrocarbyloxy group) has an oxygen-to-carbon ratio preferably in the range of 0.25 to 0.33.

WO 93/18851 PCT/GB93/00524 3 Its average molecular weight is preferably in the range of 250 to 5000, especially 300 to 400 including the terminating hydrocarbyloxy group.

That group is preferably Ci-4 (lower) alkyl or phenyl.

The divalent polyether residue is conveniently the same in oxygen-to-carbon ratio as the monovalent residue.

Its average molecular weight is preferably in the range of 150 to 1000, especially 150 to 300.

The invention provides in its second aspect a method of making the the above particular embodiment of the surfactant of the present invention which is characterised inter alia by: a plurality of copolymer chains; and (i i) on at least n-2 chains, at least one carboxylic acid group, the method being characterised by: reacting an addition-copolymer comprising carboxyl-carrying monomer units in esterifying conditions with a monovalent polyether alcohol corresponding to the monovalent polyether group, to an extent leaving at ieast one esterifiable group or at least n-2 of the addition-copolymer chains; and reacting the product of step in esterifying conditions with a divalent polyether alcohol.

The term "esterifying" includes transesterifying and the term "esterifiable" includes transesterifiable.

In this method the addition-copolymer of carboxyl-carrying and other ethylenic monomers may be a commercial ly avai lable addition-copolymer, such as SMA 3000A (Atochem UK Limited). Alternatively, the addition-copolymer may be prepared by the prior process step of copolymerising ethylenic monomers corresponding to the carboxyl-carrying and other monomers of the addition-copolymer chains. Conventional procedures using e.g. peroxide catalysts may be used.

WO 93/18851 PCT/GB93/00524 4 The copolymerisation reaction is preferably controlled to give an average molecular weight of each of the addition-copolymer chains in the relevant above ranges.

In the method of the second asoect of the invention, both reaction steps may be carried out concurrently, but preferably step is substantially completed before adding the divalent polyether alcohol.

In one variant of the latter sequential embodiment, in step some of the carboxylic groups are left for esterification in step In an alternative, a great proportion or all of the carboxyl groups are reacted in step and the divalent polyether alcohol reacts by transesterification in step The carboxyl-carrying monomer unit is preferably a 1,2dicarboxylic unit such as maleic anhydride; in such case, esterification in step with or with a derivative of an ether-terminated polyalkylene glycol), and preferably also in step is carried out by ring-opening.

The necessary control of the reaction is preferably effected by control of the proportions of the reactants.

As a result of the ring-opening and esterification only to the extent of leaving at least one esterifiable group on at least n-2 of the addition-copolymer chains, free carboxyl groups are made available.

These may be neutralised by alkali, e.g. sodium hydroxide or ammonia at 20 to 100, typically 60"C in the case of alkali) to increase solubility in water.

The relative proportions of the addition-copolymer, the monovalent polyether alcohol and the divalent polyether alcohol should be such as to cross-link at least 50 mole percent of the addition-copolymer chains, but suitably not give more than 10 of such chains per surfactant molecule, because of the resulting high viscosity.

WO 93/18851 PCT/GB93/00524 5 The proportions are preferably in defined by mole equivalent fractions of and alcoholic hydroxyl: carboxyl 0.64 hydroxyl in monovalent polyether alcohol 0.27 hydroxyl in divalent polyether alcohol 0.01 the fol lowing ranges esterifiable carboxyl 0.69 0.35 0.07.

Whether carried out concurrently or in any sequential embodiment of step and step both reaction steps are carried out at temperatures typically in the range of 140' 180 C.

A solvent, for example a hydrocarbon boiling in that range may be present, but it is usually preferred to carry it out in the melt.

One embodiment of the particular surfactant of the present invention is characterised by a carboxylic ester group having as its alcohol residue e.g. C1-20 hybrocarbyl.

Such an ester group may be incorporated in the surfactant molecule by esterification or by use of a corresponding monomer in the production of the initial addition-copolymer.

The invention in a third aspect provides a dispersion in a liquid characterised by containing a dispersion-stabilising quantity of the surfactant.

Where the dispersion is characterised by containing a dispersion-stabilising quantity of the particular surfactant of the present invent'on, the dispersion may also contain a minor proportion of a material characterised by the following features: a plurality n of addition-copolymer chains; on at least n-2 chains, at least one, especially 3-10, optionally salified carboxylic acid groups and at least two carboxylic ester groups; WO 93/18851 PCT/GB93/00524 6 at least one, especial ly 2-6 of the carboxyl ic ester groups in each chain having as its alcohol residue a monovalent polyether residue; and optionally a carboxvlic ester group having as its alcohol residue a monovalent hybrocarbyl residue, e.g.

hydrocarbyl, i.e. an uncrosslinked form of the surfactant of the present invention, which may e.g. be present in the product of the present method for the particular embodiment of the surfactant of the present invention.

The material of the discontinuous phase of the dispersion is preferably an inorganic solid, especially a crystalline oxide or combination of ox;ues, particularly having at least on its surface, a combination of a volatile oxide and an involatile oxide.

Thus the material of the discontinuous phase of the dispersion is preferably an inorganic crystalline carbonate, basic carbonate or hydroxide. It preferably has a crystallographic face similar to the 001 face of calcite. The involatile oxide component of such material of the discontinuous phase of the dispersion is preferably at least as strong a base as magnesium oxide. Other oxides include those of aluminium, copper, zinc, vanadium, cmromium, manganese, iron, cobalt and nickel and compounds which include mixtures thereof, such as clays, spinel precursors and malachites.

The dispersion is especially suitable for solid particles of high aspect ratio, for example 5:i to 50:1.

For optimal stability against flocculation and for low viscosity, where the material of the discontinuous phase of the dispersion is a crystalline solid, the distance between the carboxyl groups of the surfactant is chosen to match the crystallographic lattice parameters of the dispersed material.

WO 93/18851 PCT/GB93/00524 7 Thus, for example for the calcite lattice, the carboxyl groups in the addition-copolymer chains, are suitably separated by 4 ethylene oxide residues. It is believed that the surfactant is then substantially completely adsorbed on the dispersed phase, thereby leading to an acceptable charge density at the surface, tending to act against flocculation and for low viscosity. If the number of carboxyl groups per unit length of the surfactant molecule chains were too great, the surfactant would not be uniformly and completely adsorbed.

It is believed that, depending on the nature of the dispersed phase, the adsorption may actually be chemisorptive in nature.

However the nature of the interaction between the chains and the solid is not in any way relevant to or limiting on any aspect of the present invention.

The liquid forming the continuous phase of the dispersion typical ly is or comprises water, but may be or comprise a highly polar organic liquid. The dispersion may comprise other ingredients, such as pigments, texturising agents, perfumes and disinfectants, and other surfactants and polymers.

A preferred dispersion has a high sol ids content of 20-80% w/w, especially 25-75% w/w.

Even at such a high solids content, the dispersion may typically have a relatively low viscosity, and its rheological properties may be adjusted with considerable freedom by means of additives. In particular the dispersion of the present invention may have any rheology between mobile and thixotropic using additives.

The dispersion is suitable for coating solid substrate surfaces with the dispersed solid.

For example, a dispersion comprising fine particles is especially suitable as a printing ink of low viscosity with good stability against flocculation, e.g. for wallpapers, or for applying surface fire-proofing or making abrasive papers.

WO 93/18851 PCT/GB93/00524 8 If desired, the dispersion may be caused or allowed to settle and the precipitate may be collected and dried. The dried materie! may, o ionally after milling, be redispersed.

The material may be redispersed in an organic medium, especially a plasticised polymer.

The invention accordingly provides in its fourth aspect a composition, characterised in that it comprises a polymer containing a plasticiser and a solid dispersed material having a surfactant of the present invention adsorbed on its surface.

The polymer is especially polyvinyl chloride or a copolymer of vinyl chloride, and the plasticiser is especially a dialkyl phthalate, e.g. dioctyl phthalate.

The invention in a fifth aspect provides a method for making a dispersion according to the third aspect, characterised by incorporating with the solid a quantity of a surfactant of the present invention to adsorb onto the surface of the solid to an extent which is sufficient to stabilise a dispersion of the solid in the liquid.

Typically this is a quantity such as to adsorb onto at least half of the relevant adsorptive sites on the surface.

Incorporation of the surfactant of the present invention to adsorb onto the surface of the solid may be carried out for example by simple mixing of the surfactant of the present invention with the solid which has been pre-comminuted by wet- or drygrinding; by size reduction of the solid in the presence of the surfactant; by (co)precipitation of the solid in the presence of the surfactant; or by digestion in the presence of the surfactant of a solid previously (co)precipitated in the absence of the surfactant and/or in the presence of another surfactant.

WO 93/18851 PCT/GB93/00524 9 In each such method, incorporation of the surfactant of the present invention may include intensive mixing with the solid, for example homogenisa' ion under high shear to break down secondary aggregates of the solid and/or 'o effect further comminution.

if the surfactant of the present invention is in the form of a salt, and the nature of the interaction between the surfactant and the solid is chemisorptive, it may be desirable to include pH adjustment in the incorporation method to neutralise alkali or ammonia liberated by chemisorption of carboxylic acid groups to the solid surface.

The invention in its sixth aspect provides a redispersible solid comprising fine particles having a surfactant of the present invention adsorbed or chemisorbed on its surface.

The surfactant will be adsorbed in a quantity which is sufficient to stabilise a dispersion of the solid in a liquid, preferably sufficient to adsorb or chemisorb onto at least half of the relevant adsorptive or chemisorptive sites on the 2 surface.

The redispersible solid is are most conveniently made by drying the dispersion of the third aspect of the invention, but may be made by dry-mixing or melt-mixing of the solid with the surfactant.

5 The invention in a seventh aspect provides a method of coating a substrate with the discontinuous phase of a dispersion of the third aspect of the invention, which comprises applying the dispersion to the substrate.

Any convenient method may be used, for example intaglio 3 printing, padding, brushing, spraying, doctoring and reverseroll coating.

The process may include preliminary adjustment of the rneology of the dispersion using additives. The liquid forming the continuous phase of the dispersion typically is removed during the coating process e.g. by evaporation.

WO 93/18851 PCT/GB93/00524 10 The dispersion is especially suitable for roller-coating paper at a shear rate of less than I sec-1 The invention accordingly provides in its eighth aspect a product coated with material comprising the discontinuous phase of the dispersion of the third aspect of the invention.

Examples of such products include in particular printed papers, e.g. wallpapers, fire-proofed papers and abrasive papers.

The present invention is illustrated by the following Example.

EXAMPLE

Preparation of the surfactant The following reactants were used: 1 styrene maleic anhydride addition-copolymer (SMA) (molar ratio 3:1) of molecular weight 1900, commercially available as SMA 3000A (Atochem UK Limited); methoxy polyethylene glycol (MeOPEG), molecular weight 350; and polyethylene glycol (PEG), molecular weight 250.

The latter two reactants were dried before use by heating under vacuum.

Under a nitrogen blanket and continuing nitrogen flow, SMA (1 4 21.

4 g, 0.748 mole) and MeOPEG (995g, 2.843 mole) were 2 melted together and held at 160-165C for 1.5 to effect ring-opening and esterification of the maleic anhydride units in step of the present method. The mixture was cooled to below 125'C. PEG (49.53g, 0.2447 mole) was added and stirred in for 5 to 10 min. The whole mixture was heated to 175*C and held there for 30 to 60 min., to effect further esterification of (ring-opened) maleic anhydride units and cross-linking between the chains of the SMA addition-copolymer in step (b) of the present method.

The mixture remained liquid and of stable viscosity.

The product was cooled to 120'C and poured out.

\VO 93/18851 PCT/GB93/00524 I1 A sample was dissolved over several hours in dilute sodium hydroxide at 60"C to give a solution of salified surfactant of final pH of 7.5 to This surfactant is referred to as below.

The same procedure was used with with adjusted ouantities of the same reactants to give the surfactant referred to as below. The two surfactants are summarised and compared thus: Mole ratio SMA MeOPEG PEG Esterifiable Groups ratio C02H OH in OH in MeOPEG PEG 0.661 0.271 0.068 0.675 0.277 0.048 Surfactant A Surfactant B 3.8 3.8 0.473 0.331 Preparation of dispersion of solids in water The following aqueous slurries I and II were made up using 100g solids in aqueous solutions of surfactants made according to above: I "Ultracarb", 30% w/w solids content (RTM, commercially available from Microfine Ltd, a naturally occurring crystal I ine mineral composed of approximateLy equal amounts of huntite and hydromagnesite with a lamel lar crystal habit with an aspect ratio in the range of 5:1 to 20: 1 which consequently forms aqueous slurries of high viscosity) with Surfactant A, 1.5% w/w on Ultracarb.

I1 "Calopake 46.8% w/w solids content (commercially available from Rhone-Poulenc, a precipitated calcium carbonate of particle size 2.1 p Stokes equivalent diameter) with Surfactant B, 1.5% w/w on Calopake F.

WO 93/18851 PCT/GB93/00524 12 Addition was made stirring at first at 250 rpm, increasing to 500 rpm, as the viscosity rose; the product was stirred for a further 10 min.

dispersion was then stored at room temperature for up to 6 <ays. fhe viscosity was measured at intervals using a Brookfield viscometer at two rpm levels.

Control samples with respect to slurry I of dispersions at the same total sol ids content, using no surfactant and using each of the following known surfa'tants were also prepared and tested by the same procedures: SMA 3000A styrene maleic anhydride addition-copolymer sodium salt surfactant, Atochem UK Limited; Polysalt S polycarboxylic acid sodium salt, BASF; Coptal WA-OSN sodium dioctyl sulphosuccinate, hexylene glycol and ethylene glycol, ICI PATCO; Comparison samples with respect to slurry 1 at similar total solids content, using no surfactant and using various quantities of each of the following were also prepared and tested: Dispex N40 water-soluble polyacrylate, 0.65% w/w on water.

Coptal WA-OSN 0.8% w/w on water.

Results are set out in Tables I and 2 below TABLE 1: Brookfield viscosities cP of Ultracarb slurries Days Storage Surfactant rpm 1 2 3 4 5 6 SMA 3000A 5 25000 Poiysalt S 5 11840 11920 12'20 12800 100 1209 1218 1210 1230 Coptal WA-OSN 5 13850 13602 14520 13600 100 1668 1781 1740 1720 1 5 2520 2374 2420 2522 100 460 540 486 478 WO 93/18851 PCT/GB93/00524 13 All slurries 30% w/w solids content.

TABLE 2: Brookfield viscosities cP of Ultracarb slurries Days Storage Surfactant solids rpm 1 2 5 6 content Dispex N40 53.5 5 too thick to measure 100 too thick to measure Coptal WA-OSN 5 too thick to measure 100 too thick to measure 1 5 68 72 74 76 100 141 141 159 100 Preparation of pigmented polymer Precipitated calcium carbonate of particle size 4.5 I was aqueous slurried at a solids content of 14.9% w/w and heated with agitation to Sufficient of an 18% w/w solution of surfactant B to give 2.6% w/w surfactant on the calcium carbonate dispersed phase, was heated to 75-80'C and added to the slurry with stirring.

Stirring was continued at 85'C for 30 min. The product solid was collected on a filter, dried at 105'C for 24 h, and milled using a pin disc mill.

A control sample was made by applying 1.6% w/w of stearic acid to the precipitated calcium -carbonate by slurrying in ammonium stearate solution, then filtering, drying and milling in the same way.

All the samples of treated calcium carbonate were tested as fillers in PVC/dioctyl phthalate and PVC plastisol formulations, as follows.

A PVC masterbatch was prepared from: WO 93/18851 PCT/GB93/00524 14 Corvic P706 emulsion PVC (ICl) 406G Vinnol C8/62V paste extender copolymer containing 8% vinyl acetate (Wacker) 280g Tribasic lead sulphate 28g Polycarb S (uncoated ground calcium carbonate, 2p, ECC 20 8 g Diisononyl phthalate 1120g using a Hobart mixer.

The formulations were prepared by mixing and then triple roller-milling the following: PVC masterbatch 304g Calcium oxide 4.8g Calcium carbonate treated as above Estibond 262 polyamino adhesion promoter, AKZO The rheological properties of these formulati5ns were measured using a Carri-Med rheometer in controlled stress mode. The measuring system was a 4cm parallel plate with a 200 p gap.

A linked flow/creep shear stress programme was used with the following parameters: 0-2000 Pa shear stress sweep over 40 sec. followed immediately by creep curve at 40 Pa for 2 min, Each sample was run 3 times with satisfactory reproducibility.

Daniel gauge measurements were carried out to assess slump.

WO 93/18851 PCT/GB93/00524 15 The PVC/dioctyl phthalate formulation using surfactant B was found to have good flow properties in paste creep tests.

This gave a constant strain of 0.037 sec- 1 after sec., compared with 0.10 sec-I after 20 sec. for the control formulation using stearic acid.

The PVC plastisoi formulation using surfactant B gave a Daniel gauge measurement of Imm compared with 9mm for the control formulation using stearic acid.

In the paste creep tests, it gave a value of about 0 sec- 1 after 10 sec., compared with about 1 sec- 1 after 10 sec.

for the control formulation using stearic acid.

Its apparent viscosity at a shear stress of 2000 Pa was 5.30 Pa.s, compared with 4.76 Pa.s for the control formulation using stearic acid.

Claims (8)

1. A surfactant characterised by a plurality of addition-copolymer chains, on each chain an average of at least 0.5 adsorptive or chemisorptive groups and at least one monovalent polyether residue; and between the chains at least one divalent polyether residue.

2. A surfactant according to claim 1, characterised by the following features: a plurality n of addition-copolymer chains; on at least n-2 chains, at least one optionally salified carboxylic acid groups and at least two carboxylic ester groups; at least one of the carboxylic ester groups in each chain having as its alcohol residue a monovalent polyether residue; and at least one other of the carboxylic ester groups in each chain having as its alcohol residue a divalent polyether residue, a further end of which is the alcohol residue of the carboxylic ester group of another of said addition-copolymer chains; and optionally a carboxylic ester group having -as its alcohol residue a monovalent hybrocarbyl residue, e.g. C1-20 hydrocarbyl.

3. A surfactant according to claim 2, characterised by on at least n-2 chains, 3-10 optionally salified carboxylic acid groups and at least two carboxylic ester groups; each of 2-6 of the carboxylic ester groups in each chain having as its alcohol residue a monovalent polyether residue; and optionally a carboxylic ester group having as its alcohol residue a CI-2 0 hydrocarbyl group.

4. A method of making the surfactant according to claim 2, characterised by: reacting an addition-copolymer comprising carboxyl- carrying monomer units in esterifying conditions with a monovalent polyether alcohol corresponding to the monovalent polyether group, to an extent leaving at least one esterifiable group on at least n-2 of the addition- copolymer chains; and reacting the product of step in esterifying conditions with a divalent polyether alcohol. 0 0 0 o oo *0 0 00 *0* 0 0 0 0 0 0 0 0 0 o coo• o• *s i a A dispersion of a solid in a liquid characterised by containing a dispersion- stabilising quantity of the surfactant according to claim 1.

6. A dispersion according to claim 5, characterised in that the material of the discontinuous phase of the dispersion is an inorganic crystalline carbonate, basic 15 carbonate or hydroxide present as solid particles of aspect ratio in the range 5:1 to 50:1, the dispersion comprises a surfactant according to claim 2, and the distance between the carboxyl groups of the surfactant is chosen to match the crystallographic lattice parameters of the dispersed material.

7. A composition, characterised in that it comprises a polymer containing a 20 plasticiser and a solid dispersed material having a surfactant according to claim 1 adsorbed on its surface.

8. A method for making a dispersion according claim 5, characterised by incorporating with the solid a quantity of a surfactant according to any one of claims 1 to 3 inclusive to adsorb onto at least half of the relevant adsorptive sites on the surface.

9. A dispersible solid comprising fine particles having a surfactant according to claim 1 adsorbed or chemisorbed onto at least half of the relevant adsorptive sites on 3; RA4L 0 ATO 18 the surface. A product coated with material comprising the discontinuous phase of the dispersion according to claims 5 or 6. 0 ".i0" INTERNATIONAL SEARCH REPORT' Intarsulatal Aplcatloo Na PCT/GB 93/00524 I. CLASSLFICAT]ION OF SUBJECT MATTIM (I sevea ciasifico symbols apply, "kdiale uW6) Accoring to hteranaal Patent Qeas~ificaoo (IC or to both NadloJi Classiflaaand W pc Int.Cl. 5 C08G81/02; C08J3/24; BO1F17/52 U. FMELS SEUkCHED Mi~nimum Documeati~on Saebd7 Cluifftxar System Oazlfcatln Symbols Int.C1. 5 C08G ;COWJ 801~F ~oz~tat S=rcbe*d oerthan Minimum Doamentatmo to t~hznt tat uch aoiaouare Included in the Flaids Searcd WI. DOCUMEN4TS CONSIDERED TO BE RELEVANT' Catgor 0 r Citation of Documet, 11 with lodlicatio, were apprprat, of the rwt passages 1 Ri evt to Claim NaY'3 A EP,A,0 373 621 (NIPPON OILS AND FATS 1-8 COMPANY) June 1990 see the whole document A EP,A,O 459 651 (HI-TEK POLYMERS, INC.) 1-8 4 December 1991 see the whole document A EP,A,O 403 197 (ARCO CHEMICAL TECHNOLOGY INC.) 19 December 1990 see abstract A EP,A,O 131 558 (BERVIi( KEHI AB) 1-6,8,9 16 January 1985 see abstract; claims 1-10 0 SPeCWa categories: Of cited document to V ter document rAzLshod a&her the Intermailcal filin dae dcet enighegnalat ftxa ic orpirtdate and Not In oeflict with the appilcatIoa hot ''dcnde a to e e e w of the artrehichnis m cited t udrstand the principle or theory underlying the 'V eaier document but puibli"oor wthed 000?nso -Z docamost of pattiwular eakvance; the chimed Inventloc filig da~te annot be ronsidered novl or cannot be cousldered to LV document wich tay thrgw doubtsl ty clawms) or IWve an invootive spep which it cited to estallzh the P cc0 ditte Of another "rdocument of portcl rolevence; the claimed Inventiob citation or other special reaso (as specified) canot be cathdere to Itrolve a inveotive step wben the' '0 document refet. ng to an oral disclosure, use, vhlbition or document Is combined with aue or more other such docu- other means DMsdcmb en wu oapro ie 'r documenat publihed prior to the Intenu~ nale filing date butintea later then the priority date claimned W' documest meraher of the same pltant family 2 V. CIXTlFCATION Date of the Actual Completon of the International Search Date of Maing of this lntornslicea Search Ropot 26 AUGUST 1993 06. 090, Inteanccal searching Authority Slpuore of AutthortUz Officer EURlOPEAN PATENT OFFCE W.H.F. FISCHER Form PCrII5AM2O (ca Am) Jntr LU PCT/GB 93/00524, Internatioal Ap~kidoa No ilL DOCLIMTS CONSIDERlED TO BE RELEVANT (CONTINED FROM THE SECOND SILEEr) Caz~~y Oaion of Document, wMt LodIc1Ioa, where a~opdtle, of the rokmwut passages Relevant to Qaha No. A EP,A,O 064 225 (HOECHST AG) 7-10 November 1982 see the whole document A EP,A,0 233 684 (IMPERIAL CHEMICAL 5-10 INDUSTRIES PLC) 26 August 1987 see abstract; examples 46-107 16Pa PCT/tSA210 (exta 4We) (Jw 1"S) ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. 9300524 71162 This m= ists the pateat family mnunhas rmisting to the ptent document cited in the above-mentioned intrtunional war rqorL The membas ne as contained in the European Patent Office EDP file on The European Patent Office is in no ray liable for these particulars which arenerly given for the purpose of inforation. 26/08/93 Pateme docteet Publication Patent family PubriczAdon cited in wearch report date monbe(s) dae EP-A-0373621 20-06-90 JP-A- 2163108 22-06-90 US-A- 5142036 25-08-92 EP-A-0459651 04-12-91 US-A- 5061742 29-10-91 AU-B- 632026 10-12-92 AU-A- 7702791 21-11-91 JP-A- 4227748 17-08-92 EP-A-0403197 19-12-90 AU-B- 635538 25-03-93 AU-A- 5752190 20-12-90 CA-A- 2018186 16-12-90 JP-A- 3035015 15-02-91 US-A- 5194493 16-03-93 EP-A-0131558 16-01-85 SE-B- 450691 20-07-87 US-A- 4634450 06-01-87 AU-A- 3025484 10-01-85 CA-A- 1231032 05'-01-88 JP-A- 60068040 18-04-85 SE-A- 8303863 07-01-85 EP-A-0064225 10-11-82 DE-A- 3116581 30-12-82 JP-A- 57182360 10-11-82 US-A- 4389213 21-06-83 EP-A-0233684 26-08-87 AU-A- 6780387 06-08-87 CA-A- 1272727 14-08-90 JP-A- 62201927 05-09-87 8I For mor dtiis about thisi anCX 6Ce Offiial JOUrl of heuropan Patent Offi, No. 12182