Patent Application: US-201113078576-A

Abstract:
the present invention relates to the use of ab block copolymer composition as a surface coating wherein the composition comprises an ab block copolymer ; and a liquid medium and wherein the ab block copolymer comprises : a substantially hydrophobic block a , and a substantially hydrophilic block b wherein the hydrophobic block a comprises one or more monomer of formula wherein r is h or c 1 to c 4 alkyl ; z is o , p or n ; and r ′ is selected from the group comprising : c 1 to c 18 linear or non linear alkyl ; c 1 to c 18 alkylamino alkyl ; c 1 to c 18 dihydroxyalkyl ; c 1 to c 18 silylalkyl ; epoxy alkyl , phosphoryl or phosphoryl alkyl ; a styrene based monomer ; a vinyl phosphonate or phosphoric acid monomer ; and wherein the liquid medium comprises either : water ; an organic solvent ; an organic solvent substantially free from water ; or an organic solvent and water ; and wherein : the liquid medium further optionally comprises one or more additive , surfactant or wetting agent .

Description:
the embodiments of the present invention described below are not intended to be exhaustive or to limit the invention to the precise forms disclosed in the following detailed description . rather , the embodiments are chosen and described so that others skilled in the art may appreciate and understand the principles and practices of the present invention . preparation of polymers and block copolymers according to the present invention to manufacture the ab diblock copolymers of the present invention a controlled polymer or copolymer synthetic process is required in order to achieve a product with the required properties of , for example , desired molecular weight and narrow weight distribution or polydispersity . polymers with a narrow molecular weight distribution are able to possess and exhibit substantially different properties to polymers prepared by conventional means . living radical polymerizations ( also sometimes referred to as controlled free radical polymerizations ) provide a maximum degree of control for the synthesis of polymers with predictable and well - defined structures . recently , controlled / living radical polymerization ( clrp ) has been shown to be a viable technique for the preparation of a large and diverse range of materials with precisely tailored nano - and micro - scale features . group transfer polymerisation ( gtp ), atom transfer radical polymerization ( atrp ), nitroxide - mediated polymerization ( nmp ), reversible addition fragmentation transfer polymerization ( raft ), and madix all form part of these recently developed techniques and even more recently , activated regenerated by electron transfer ( arget ). these methods allow the synthesis of a large variety of polymeric architectures such as block copolymers , graft copolymers , stars , star - blocks , miktoarm stars or macromolecular brushes . importantly , a controlled polymerisation process is required for controlling the molecular structure of synthetic polymers , and thus for controlling the size of micellar aggregates in solution . indeed , the aggregate sizes of polymers depend directly on the exact nature of the polymer ( that is for example ; molecular weight , length of polymer , and ratio between hydrophobic and hydrophilic blocks ). whilst the presently described example prepares a block copolymer using the raft agent , cpdb ( 4 - cyanopentanoic dithiobenzoate ), it will be appreciated that other raft agents may be used . similarly , the block copolymers of the present invention may be prepared by means of other controlled living polymerisation techniques as previously mentioned above . for example when using group transfer polymerisation ( gtp ), the polymerisation reaction as described in s . p . rannard , n . c . billingham , s . p . armes and j . mykytiuk , european polymer journal , 1993 , vol 29 p 407 . “ synthesis of monodisperse block copolymers containing methacrylic acid segments by group - transfer polymerization : choice of protecting group and catalyst ”; may be followed , the relevant section of which is incorporated herein by reference . for example when using atom transfer radical polymerization ( atrp ), the polymerisation reaction as described in : arrainen , amilcar pillay ; pascual , sagrario ; haddleton , david m . ; journal of polymer science , part a : polymer chemistry ( 2002 ), 40 ( 4 ), 439 - 450 . “ amphiphilic diblock , triblock , and star block copolymers by living radical polymerization : synthesis and aggregation behaviour ” may be followed , the relevant section of which is incorporated herein by reference . when using nitroxide - mediated polymerization ( nmp ), the polymerisation reaction as described in : wo 2007 / 057620 a1 ( arkema ); “ method for preparing a living polymer comprising methacrylic and / or methacrylate units ” may be followed , the relevant section of which is incorporated herein by reference . however , it will be appreciated by one skilled in the art that modifications may be appropriate to the above methods to prepare a target polymer . in a first step , the following conditions were used for the synthesis of pbuma with a targeted polymerization degree of 15 . nbuma ( 5 . 01 g , 35 . 24 mmol ), 4 - cyanopentanoic dithiobenzoate ( cpdb ) ( 0 . 518 g , 2 . 34 mmol ), aibn ( 0 . 19 g , 1 . 18 mmol ) and propan - 2 - ol ( solvent , 8 . 45 g , 60 % in mass ) were introduced in a 250 ml round bottom flask containing a magnetic stirrer . the reaction flask was degassed by nitrogen bubbling for 20 minutes at 0 ° c . and then heated at 75 ° c . in a thermostated oil bath under a nitrogen atmosphere . after 5 hours of polymerization , a sample was withdrawn to analyze by 1 h nmr and thus calculate the conversion of buma . in a second step , a solution containing maa ( 24 . 2 g , 0 . 28 mmol ), aibn ( 0 . 20 g , 1 . 25 mmol ) and propan - 2 - ol ( solvent , 70 . 2 g , 75 % in mass ) was prepared in a second round bottom flask . this solution was degassed by nitrogen bubbling for 20 minutes at 0 ° c . and was then transferred via a cannula to the reaction flask . after stirring for 17 hours at 70 ° c ., the reaction was cooled via an ice bath in order to stop the polymerisation . a total conversion of maa was determined by 1 h nmr spectroscopy in dmso at 400 mhz , integrating one vinylic proton ( at 5 . 9 to 6 ppm from maa ) in comparison with the peak at 12 . 3 ppm corresponding to cooh from both the monomer and the polymer ). the polymer was then purified by precipitation in diethyl ether . the recovered polymer pbuma 15 - b - pmaa 119 was dried in a vacuum oven overnight at 40 ° c . in a first step , pbuma 15 was prepared as previously described above from a mixture of nbuma ( 2 . 56 g ), cpdb ( 0 . 26 g ), aibn ( 0 . 09 g ) and propan - 2 - ol ( solvent , 4 . 52 g , 60 % in mass ). the polymerisation was allowed to proceed for 5 hours at 75 ° c . and a conversion of 95 % obtained by 1 h nmr in cdcl 3 . in a second step , a degassed solution containing tmacma ( 19 . 72 g ), dmaema ( 11 . 43 g ), aibn ( 0 . 09 g ) and propan - 2 - ol ( 35 . 23 g ) was transferred via cannula into the reaction flask containing pbuma 15 . after stirring for 17 hours at 70 ° c ., the reaction was cooled in an ice bath in order to stop the polymerisation . a total conversion of tmacma and dmaema was determined by 1 h nmr spectroscopy in dmso . the polymer was then purified by precipitation in cold hexane . the recovered polymer pbuma 15 - b - p ( tmacma 60 - co - dmaema 61 ) was dried in a vacuum oven overnight at 40 ° c . the same procedure as described above was followed for the synthesis of the copolymer pbuma 15 - b - pdmaema 120 using the appropriate starting materials . in a first step , p ( buma 15 - co - deaema 15 ) was prepared following the same procedure as for the preparation of pbuma 15 above but using instead a mixture of nbuma ( 2 . 53 g ), n , n - diethylaminoethylmethacrylate ( deaema , 3 . 36 g ), cpdb ( 0 . 26 g ), aibn ( 0 . 09 g ) and propan - 2 - ol ( solvent , 4 . 25 g , 60 % in mass ). the polymerisation was allowed to proceed for 5 hours at 75 ° c . in a second step , a degassed solution containing dmaema ( 22 . 13 g ), aibn ( 0 . 09 g ) and propan - 2 - ol ( 38 . 75 g ) was transferred via cannula into the reaction flask containing p ( buma 15 - co - deaema 15 ). after stirring for 24 hours at 70 ° c ., the reaction was cooled in an ice bath in order to stop the polymerisation . the complete conversion of the reactants was determined by 1 h nmr spectroscopy in dmso . the polymer was then purified by precipitation in cold hexane . the recovered polymer p ( buma 15 - co - deaema 15 )- b - pdmaema 120 ) was dried in a vacuum oven overnight at 40 ° c . in a first step , the following conditions were used for the synthesis of pbuma with a targeted polymerization degree of 15 . nbuma ( 15 . 01 g , 0 . 1 mol ), styrene ( 1 . 12 g , 10 . 7 mmol ), blocbuilder ® ( 2 . 68 g , 7 . 03 mmol ), and propan - 2 - ol ( solvent , 8 . 49 g , 70 % in mass ) were introduced in a 500 ml round bottom flask equipped with a mechanical stirrer . the reaction flask was degassed by nitrogen bubbling for 20 minutes at 0 ° c . and then heated at 75 ° c . in a thermostated oil bath under a nitrogen atmosphere . after 8 hours of polymerization , a sample was withdrawn to analyze by nmr and thus calculate the conversion of buma ( conversion 73 %). at the end of this step , the reaction was left to cool down to 50 ° c . then , propan - 2 - ol ( solvent , 171 . 5 g ) was added . the mixture was kept under stirring at room temperature overnight . in a second step , maa ( 73 . 4 g , 0 . 85 mol ), styrene ( 7 . 41 g , 71 . 2 mmol ) and aibn ( 0 . 57 g , 3 . 48 mmol ) were added to the previous mixture . the reaction mixture was degassed by nitrogen bubbling for 20 minutes at 0 ° c . after stirring for 4 hours at 75 ° c ., a conversion of 92 % in maa was determined by 1 h nmr spectroscopy in dmso at 400 mhz , integrating one vinylic proton ( at 5 . 9 to 6 ppm from maa ) in comparison with the peak at 12 . 3 ppm corresponding to cooh from both the monomer and the polymer ). ipa was evaporated and the recovered polymer pbuma 15 - b - pmaa 119 was dried in a vacuum oven overnight at 40 ° c . in a first step , pbuma 15 was prepared following the same procedure as for the preparation of pbuma 15 above but using instead a mixture of nbuma ( 13 . 6 g ), styrene ( 1 . 1 g ), blocbuilder ® ( 2 . 42 g ), and propan - 2 - ol ( solvent , 5 . 8 g , 75 % in mass ). the polymerisation was allowed to proceed for 8 hours at 75 ° c . in a second step , dmaema ( 59 . 7 g ), tmacma ( 105 . 2 g ), styrene ( 7 . 3 g ), aibn ( 0 . 52 g ) and propan - 2 - ol ( solvent , 155 . 7 g ) were added to the reaction flask . the mixture was degassed by nitrogen bubbling for 20 minutes at 0 ° c . after stirring for 4 hours at 75 ° c ., the polymerization was stopped . ipa was evaporated and the recovered polymer pbuma 15 - b - pmaa 119 was dried in a vacuum oven overnight at 40 ° c . the same procedure as described above was followed for the synthesis of the copolymer pbuma 15 - b - pdmaema 120 using the appropriate starting materials . a polymer or polymeric composition prepared according to the present invention may be coated onto a preferred substrate as described hereafter by any established coating process , for example , but not limited to for example a spray process . generally , the treatment process involves the following steps : step ( 1 ): dissolution of the copolymer molecules in water or in a mixture of alcohol / water at a desired ph and salt conditions under gentle agitation . typically the system is left to equilibrate for 24 hours . the copolymers chosen are usually not of a high molecular weight ( for example the copolymers typically have a range of between 2000 to 100000 g / mol ) and such molecules equilibrate rapidly when dissolved in an aqueous solution or in a mixture of alcohol / water . solvents suitable for use in the composition of the present invention are preferably as previously described . in the following experimental procedure , the copolymer systems were left for 24 hours simply to be certain that the systems were fully equilibrated . however , the system was also found to equilibrate within much shorter timescales . for example , in pure ethanol the copolymer system was ready to use after just two hours of stirring . in a mixture of water ( 92 % w ) and ethanol ( 8 % w ), it was necessary to first fully dissolve the polymer in ethanol for two hours and then to add the polymer to water and mix the system again for at least one further hour . agitation of the copolymer systems was required during the process of dissolution and mixing , but it was not found to be critical and simply slowly stirring the copolymer system was found to be sufficient . the length of time for agitation depended on the solvent system . step ( 2 ): exposure of the substrate of interest to the copolymer solution , that is , applying the solution to a desired substrate . whilst not wishing to be bound by any particular theory , evidence from the present invention implies that adsorption is complete after a few minutes . methods of exposing the substrate to the solution include for example any known technique for forming a coating from a solution such as spin coating , dip coating , roller coating , brush coating , curtain flow or spraying , roller coating , wire - bar coating , extrusion coating , air knife coating , curtain coating , slide coating . more preferably dipping and spraying ensures that every part of the surface has been wetted by the treatment composition . preferably the treated surfaces need to be dried after applying the treatment composition . this can be achieved at room temperature or at higher temperatures , but if higher temperatures are used the drying time should be reduced . it should be noted that the drying temperature does not enhance the performance of the coating ; rather it shortens the drying time of the treatment . drying in ambient conditions will only lengthen the drying time . various surfaces may be treated including for example metal , metal alloys , glass , plastics , rubber , porcelain , ceramic , tile , enamelled appliances , polyurethane , polyester , polyacrylic , melamine / phenolic resins , polycarbonate , painted surfaces , natural surfaces like wood , cellulose substrates , and the like . 1 ) the metal or metal alloy object or articles may be comprised of a metal or metal alloys selected from the group comprising : aluminium , magnesium , beryllium , iron , zinc , stainless steel , nickel , nickel - cobalt , chromium , titanium , tantalum , rare earth metal , silver , gold , platinum , tungsten , vanadium , copper , brass , bronze and the like or combinations or derivatives thereof or plated articles thereof 2 ) the plastic objects or articles may be comprised of polymers selected from the group comprising : transparent or non - transparent polyurethane , polycarbonate , polyethers , polyesters , polyvinyl chloride , polystyrene , polyethylene , polyvinyl acetate , silicone rubbers , rubber latex , polycarbonate , cellulose esters polycarbonate , polyester - polyether copolymers , ethylene methacrylates , polyolefins , and the like , silicone , natural and synthetic rubbers , nylon , polyamide or combinations thereof 3 ) the glass objects or articles may be comprised at least partially of : glass , such as optical glasses , optical lenses , polarizing glasses , mirrors , optical mirrors , prisms , quartz glass , ceramics and the like or combinations thereof . the substrate may include an exterior surface or article member , such as for example : a window sash , structural member or windowpane of a building ; an exterior member or coating of a vehicle such as automobile , railway vehicle , aircraft and watercraft ; an exterior member , dust cover or coating of a machine , apparatus or article ; and an exterior member or coating of a traffic sign , various display devices and advertisement towers , that are made , for example , of metal , plastics , glass , a combination thereof and other materials . examples of substrates , include , but are not limited to : medical devices , protection shields , window sheets , windowpane , greenhouse walls , freezer doors , food packaging foils and printing paper . 1 ) the metal objects can include for example : freezer doors , mirrors , condenser pipes , ship hulls , underwater vehicles , underwater projectiles , airplanes , wind turbine blades and the like . 2 ) the plastic objects can include for example : face shields , helmet shields , swim goggles , surgeon face shields , food packaging , plastic foil , greenhouse walls , greenhouse roofs , mirrors , wind shields , underwater moving objects , airplane windows , shields , and the like . 3 ) the glass objects can include for example : window glasses , greenhouse , glasses , glass sheets , face shields , optical glasses , optical , lenses , polarizing glasses , mirrors , optical mirrors , prisms , quartz glass , parabolic antennas , automobile head beam light glasses , automobile windshields , airplane control light glasses , solar panels , runway lights and the like . the coating may also be applied on clear plastic or glass used for example as protective shields , windows , windshields , greenhouse panels , food packaging foils , goggles , optical glasses , contact lenses and the like . likewise the coating may be applied for example : on an exterior surface of a telescope lens , especially a riflescope , a spotting scope , or a binocular to reduce the likelihood of fogging or distortion due to the collection of moisture on the lens without significantly reducing light transmission through the lens in the visible range . that is , scopes used by sportsmen , the military and the like . exterior or interior parts of a building may also benefit form the coating for example : windowpanes , toilets , baths , wash basins , lighting fixtures , kitchenware , tableware , sinks , cooking ranges , kitchen hoods and ventilation fans , which are made from metal , glass , ceramics , plastics , a combination thereof , a laminate thereof or other materials . “ easy - to clean ” and dirt / dust repellent ” properties of a surface treatment according to the present invention a surface treatment containing the polymer pbuma 30 - b - pmaa 119 was applied to one half of one side of a polyester powder coated aluminium panel . the panel was then placed in the bottom of a box containing a soiling material ( for example garden soil with a mixture of several components such as clay , sand , formic acid , organic residues from plants ). the panel was placed well beneath the soiling material . the box was attached to an electronic orbital shaker and was shaken for 30 seconds at a rate of 640 revolutions / minute . the panel was then removed from the box and tapped twice on a hard surface to remove excess soiling . photographic images and visual observations were recorded ( fig1 a , 1 b and 1 c ). the panel was then rinsed by spraying with 20 ml tap - water and allowed to dry . this process was considered as one dirt cycle and was repeated up to 5 times . as seen in fig1 , the treated side ( bottom of the picture ) looks cleaner than the untreated side ( top of the picture ) of the panel . indeed , it can be clearly seen that the dirt / dust that has been deposited and stacked on the untreated side remains whereas there is no deposit on the treated part of the panel . besides the visual observation and pictures seen in fig1 , colour measurements were recorded using a spectrophotometer after each dirt cycle to evaluate the colour difference δe between the surface prior to exposure to the dirt ( that is , a clean surface ) and the surface after exposure to dirt ( that is the dirty surface ). the difference between the two surfaces is illustrated in fig2 which shows a comparison of the total colour difference δe of the soiled panels . the colour difference is calculated from the cie 1964 colour system . the system considers the lightness l *, the red - green value a * and the yellow - blue value , b *. δ e =( δ l 2 + δa 2 + δb 2 ) 1 / 2 equation 1 δ l = l 1 − l 2 , δa = a 1 − a 2 , δb = b 1 − b 2 and δl , δa , δb are the colour differences in cie l * a * b * colour space l 1 , a 1 , b 1 are the l * a * b * values for sample 1 ( clean panel before soiling ) l 2 , a 2 , b 2 are the l * a * b * values for sample 2 ( panel after soiling or rinsing ) after soiling , the colour difference δe is less for the treated panels than for untreated panels . this corresponds to less initial soil adhesion on the treated panels , even after five dirt cycles . this demonstrates clearly that the surface treatment according to the present invention , once coated onto a surface provides “ dirt repellent ” properties compared with an uncoated surface . fig9 illustrates the visual rating of performance or polymer coverage versus the number of water rinses to demonstrate the longevity of the “ wetting effect ” of the surface treatment applied polyester powder coated aluminium panels . fig9 also illustrates the results for several polymers from fig9 it can be seen that the non - fluorinated ( either anionic or cationic ) ( nf - ap or nf - cp ) copolymers perform as well as the fluorinated copolymer derivative . that is , there is no loss in terms of performances using a copolymer which is more easily dispersed or solubilised in water ( see example 8 for the solubility comparison of the fluorinated and the non - fluorinated copolymers ) and which address environmental / health concerns . in addition , it can be seen that it is possible to ‘ tune ’ the longevity of the effect by ‘ tuning ’ the composition of the polymer which is utilised depending on the target application . in fig9 , f cp ( 30 / 120 ) is ptfema 30 - b - pdmaema 120 nf cp ( 30 / 120 ) is pbuma 30 - pdmaema 120 nf cp ( 15 , 15 / 120 ) is ( p ( buma 15 - co - deaema 15 )- b - pdmaema 120 nf cp ( 15 / 60 , 61 ) is pbuma 15 - b - p ( tmacma 60 - co - pdmaema 61 ) f ap is ptfema 30 - pmaa 120 nf ap is pbuma 30 - pmaa 120 fig1 illustrates the wettability performance of selected polymers on two substrates : i ) a polyester powder coated aluminium panel and ii ) a glass slide . both substrates were treated with a surface treatment containing the polymer buma 30 - maa 119 . it can be clearly seen in fig1 that depending on the substrate selected , and therefore depending on the target application , the longevity of the effect maybe be tuned . fig1 illustrates the performance of a surface treatment according to the present invention in comparison with commercially available products . listed below are the compositions of known products a and b . product commercially available a has the following ingredients : aqua , propylene glycol butyl ether , alcohol denat ., ethanolamine , cocamidopropyl hydroxysultaine , parfum , benzalkonium chloride , alkyl dimethyl ethylbenzyl , ammonium chloride , tartrate , sodium chloride . product commercially available b has the following ingredients : aqua , c9 - 11 pareth - 3 , sodium cumenesulfonate , sodium carbonate , parfum , sodium diethylenetriamine pentamethylene phosphonate , sodium palm kernelate , sodium dodecylbenzenesulfonate , sodium citrate , acrylic acid diquat copolymer , dipropylene glycol , lauramine oxide , benzisothiazolinone , butoxydiglycol , sodium hydroxide , sodium chloride , colorant , geraniol , limonene , linalool . 1 . known product a only . 2 . known product b only . 3 . a mixture of the known product a and the polymer pbuma 30 - b - pdmaema 120 at a concentration of 0 . 5 g / l 4 . a mixture of the known product b and the polymer pbuma 30 - b - pdmaema 120 at a concentration of 0 . 5 g / l all of the panels were then rinsed with sprayed tap water for 30 seconds . a visual rating was allocated . a rating of 5 means very good wettability , a rating of 1 means poor wettability . it can be seen from fig1 that the use of a polymer according to the present invention provides improved performance . the surface treatment was also tested in a bathroom as seen in fig3 . in fig3 , a shower door has been half treated with a water - based treatment containing the polymer pbuma 15 - b -( tmacma 60 - co - dmaema 61 ). after exposure to a shower in which shampoo and soap had been used , it was clearly observed that the treated side ( left side on fig3 ) was much cleaner that the untreated side ( right side fig3 ). indeed , it can be observed that organic residues ( from shampoo and soap ) and insoluble mineral deposits ( from hard water ) have adhered and dried on the untreated side of the shower door whereas , no deposits or ‘ build - up ’ of material are present on the treated surface . accordingly , this illustrates that the surface treatment reduces the appearance , formation , adhesion and build - up of insoluble mineral deposits , limescale , rust and soap scum when water is allowed to evaporate off most siliceous and non - siliceous surfaces . therefore , it is clear that the surface treatment according to the present invention provides superior “ easy - to - clean ” results . panels were first cleaned in soap solution , rinsed with deionised water and then dried with a lint free tissue . the panels were half treated with a surface treatment comprising the polymer pbuma 15 - pmaa 119 . the treated substrates were exposed to continuous water spray for 30 seconds . when observed , the treated side was totally wetted by the water and demonstrated homogeneous coverage of the polymer with no degradation in performance , whatever the substrate , as seen on fig4 a ( pvc substrate ) and fig4 b ( polyester powder coated aluminium panel ). similar results were obtained with a treatment containing a cationic polymer pbuma 15 - b - p ( tmacma 60 - co - pdmaema 61 ), as seen in fig5 a ( pvc substrate ) and fig5 b ( painted aluminium panel ). accordingly , it is also clear that the surface treatment according to the present invention provides a substrate with a good “ water - sheeting ” behaviour . a surface treatment comprising the polymer buma 15 - maa 119 was applied on a polyester film which was used in food packaging ( fig6 a ) and on a glass mirror ( fig6 b ). the treated substrates were exposed to water vapour rising from a beaker containing tap water heated at 85 ° c . it was clearly observed that the treated side of the surface was totally fog free ( that is , it was completely transparent ) whereas on the untreated side of the surface , small droplets formed which produced poor visibility through the film . similar results were obtained with a treatment comprising the cationic polymer pbuma 15 - b - p ( tmacma 60 - co - dmaema 61 ), as seen in fig7 ( polyester film ). accordingly , it was evident that the surface treatment according to the present invention provides “ anti - fog ” properties . fig8 illustrates the same panel as in fig4 b but after drying vertically at room temperature . on the untreated side ( right ), dried watermarks were observed leading to an unpleasant appearance or finish ; whereas on the treated side ( left ) no drying - marks were present . this demonstrates the “ spot - free finish effect ” provided by using a surface treatment according to the present invention . investigates the “ antibacterial and anti - fungal ” properties of a substrate treated with the block copolymer of example 1 a solution of pbuma 15 - b - p ( tmacma 60 - co - dmaema 61 ) ( nf cp 15 / 60 , 60 ) in ethanol was evaluated as an anti - bacterial and / or anti - fungal surface treatment in addition to its ability to promote water sheeting ( fig9 ). the test was conducted as follows . ceramic tiles ( 100 × 100 mm ) were sterilised using alcohol in a laminar flow cabinet . two sterile tiles were then coated liberally with 2 ml of a solution of nf cp copolymer and allowed to air dry . the treated tiles and untreated control tiles were then assessed for the protection of the surface to microbial attack as detailed below . one treated tile and two untreated tiles were surface inoculated with 1 ml of bacteria as detailed below in a laminar flow cabinet . the inoculum was spread over the tile surfaces using sterile l shaped spreaders and allowed to air dry . one of the untreated tiles was swabbed to determine the number of colony forming units per tile by serial dilution and plate counting . the treated and untreated tiles were then washed by pouring 100 ml of sterile water over the tile surface and the number of surviving bacteria was determined by serial dilution and plate counting . the washed tile surface was then swabbed , which was serially diluted and plate counted to determine the colonies remaining on the tiles . this procedure was repeated using a fungi system as detailed below in table 2 . the sample coated onto the surface of ceramic tiles resulted in lower numbers of colonies being recovered ( surviving ) after the wash and swab . the total reduction in the number of colonies was 54 . 32 % for bacteria and 28 . 05 % for fungi . on the control ceramic tile showed there was no reduction in bacteria with a lower reduction of 15 . 53 % for fungi . therefore the laboratory tests indicate that when a polymer coating is applied as a surface coating to ceramic tiles according to the present invention there seems to be an effect on the levels of bacteria and fungi inoculated onto the surface . analysis of the concentration of copolymers in a water - based formulation using the non - fluorinated block copolymer of example 1 in comparison to a fluorinated copolymer the use of non - fluorinated copolymers facilitates the preparation of fully aqueous formulations in comparison to fluorinated copolymers . indeed , whereas ptfema 30 - b - pmaa 120 ( f - ap 30 / 120 ) is not soluble in water , it has been possible to solubilise pbuma 15 - b - pmaa 120 ( nf - ap 15 / 120 ) directly in water without using for example ethanol or surfactants . depending of the use of surface treatments , the concentration of copolymers required may vary . using non - fluorinated copolymers can lead to a broader range of concentrations available in water based surface treatments . the following table gives the maximum concentration ( g / l ) of copolymers f - ap and nf - ap in denaturated ethanol ( ims ) and in water - based formulation . the water - based formulation was prepared by adding 5 ml of the solution of copolymers in ethanol at the maximum concentration into 45 ml water . therefore , the water - based formulation contained 10 wt % alcohol . the maximum working concentration in a water based formulation can be eight times greater for the non - fluorinated polymer compared to the maximum working concentration for the fluorinated polymer . water - based surface treatments were prepared using nf - ap ( 15 / 20 ), f - ap ( 30 / 120 ) and as a comparison different commercially available existing additives and using two surfactants , brij 30 and glucopone cs 215 , to facilitate the spreading of treatments on the tested substrates , in this experiment white - powder coated aluminium q - panels . the concentration of each surfactant was 0 . 5 g / l . the existing additives were used at concentrations of 5 g / l , which is the recommended concentration advised by the suppliers . the copolymer of the present invention was used at 10 - times lower concentration , 0 . 5 g / l in a water - based formulation containing 8 wt % ethanol . the table 7 summarises the content of each of the surface treatment formulations used in this comparison . each formulation was applied to a q - panel by the flow - coating method of application and after drying , tap - water was sprayed onto the surfaces following the same procedure as described in example 4 . a rating of 5 means very good wettability and water spreads readily over the panel , a rating of 1 means poor wettability and water beads on the panel . the results for 12 wetting cycles are shown in fig1 . fig1 shows that the surface treatment comprising nf - ap ( 15 / 120 ) diblock copolymers performs as well as f - ap ( 30 / 130 ) copolymers in terms of water wetting properties and does not have any of the environmental constraints of f - ap ( 30 / 130 ). comparing the formulations prepared using the competitor additives , the surface treatment comprising additive 1 is the only formulation that achieves similar ratings to nf - ap ( 15 / 120 ). this however , is only achieved by using a much higher concentration of additive compared to the concentration of nf - ap ( 15 / 120 ) copolymers . formulations prepared with additives 2 and 3 show a lesser wetting effect than the surface treatments using nf - ap ( 15 / 120 ) and in particular , show a shorter longevity . the water sheeting properties of the non - fluorinated product nf - ap performs as well as the fluorinated product f - ap and does not possess any of the environmental constraints associated with using fluorinated products . the only competitor product that displays similar performance to nf - ap is the formulation made with additive 1 . the usage rate of this additive is , however , 10 times greater than nf - ap and therefore its use has a larger negative impact on the environment . this comparison demonstrates that there is an opportunity and requirement to improve stay - clean surface treatment products . the present invention therefore provides novel uses of ab block copolymers which are able to self assemble into aggregate structures either in water , in a water / alcohol mixture or in a pure alcohol dispersion , for the preparation of a surface treatment which provides a functional coating , that includes the following properties and advantages and provides a surface coating or a surface treatment that imparts one or more functional effects : ( i ) a coating that repels dust and dirt , that is , the coating reduces the adhesion and hence the build - up / depositition of soil / dust and dirt in order to provide a coated surface with a cleaner appearance and also a coating that is easier to clean . ( ii ) a coating that has improved water - sheeting behaviour ; meaning that water does not de - wet or experience beading on the surface , rather the water forms a continuous sheet meaning that the surface is wetted by water easily ; in other words provides good water wettability . ( iii ) a coating that once applied to a surface prevents the build - up of crystalline scale deposits and the associated surface fouling effects that are visible with the build - up of lime scale . the surface treatment is able to reduce the appearance and prevent the build - up and deposition of lime scale . the formation of crystalline deposits due to chemicals present in water which build up over a period of time , particularly in bathrooms , toilets , sinks and particularly in places where there are flows of domestic tap water , are also reduced . ( iv ) a coating that is able to provide ‘ anti - fog ’ properties . a haze , mist or fog is defined as the formation of small droplets of water on a transparent surface in the presence of water vapour that results in the transparency of the surface being reduced . consequently , the terms “ anti - hazing ”, “ anti - mist ”, “ anti - fogging ”, “ fog resistance ” or “ fog up free ” properties refer to the properties of a transparent surface which has been treated in such a way so that in the presence of water vapour either : ( 1 ) beads of water are not able to form on the surface and instead water vapour on contact with the surface forms a thin continuous sheet in the form of a film at the surface which is transparent ; or ( 2 ) water is repelled on contact with the surface which results in beads which have the ability to readily roll off the surface . in both cases , the haze which is caused by the formation of small droplets of water on a surface in the presence of water vapour is reduced . more specifically , the use of a hydrophilic surface treatment according to the present invention means that when the coating is applied to a surface for example , but not limited to : metal , glass or plastic surfaces , the surface coating or a surface treatment prevents water droplet formation on the selected surfaces when the surfaces are exposed to conditions which can lead to the ‘ fogging ’ of the surface . such conditions include for example : the exposure of the surface to air of high humidity , the exposure of the surface to water vapour or the transfer of the surface from a low temperature environment to a higher temperature environment causing the surface to ‘ fog up ’, that is the surface becomes clouded by condensation formed from the cooling of water alighting on the surface . the applied hydrophilic surface treatment of the present invention is useful for preventing water condensation or fogging on metallic , plastic , and glass surfaces and the like . that is , the applied hydrophilic surface treatment of the present invention does not prevent water condensation , but water that has condensed forms a continuous sheet rather then beads . as an aside , when the selected surface coating or surface treatment is clear plastic or glass , the treatment applied to the surface ensures that these particular surfaces maintain a good transparency . ( v ) in addition it has been found that the combination of the durable hydrophilic effect and the fast and uniform drying effect of the polymeric surface coating or surface treatment of the present invention provides treated substrates with ‘ anti - spotting ’ properties and therefore provides treated surfaces with an aesthetically pleasing finish , that is a treated surface has a ‘ spot - free ’ finish , more specifically a treated surface which does not display the appearance of water - marks , even after the treated surface has been contacted at a later point in time with water . a further feature of the presently claimed surface coating or surface treatment is that the treatment may be applied to a wide range of substrate surfaces , for example but not limited to : plastic , metal or other materials . it has been found that the hydrophilic surface treatment of the present invention adheres ‘ strongly ’ to for example surfaces that include : metals , metal alloys , glass , plastics , rubber , porcelain , ceramic , tile , enamelled appliances , polyurethanes , polyesters , polyacrylics , melamine / phenolic resins , polycarbonates , painted surfaces , and wood . consequently , the hydrophilic surface treatment of the present invention finds particular use in a wide range of application areas such as for example ; building and diy treatments , the car industry for the treatment of interior and exterior metal and glass , bathroom and wet room applications , and general household surface cleaning products . the treatment also finds use in other application areas such as for example but not limited to : the food packaging and foils industry , and as protective shields . fogging is a phenomenon observed commonly in applications of plastic films in the food packaging and agricultural sectors . the term ‘ fog ’ used herein describes the condensation of water vapour , in the form of small discrete water droplets , creating a translucent appearance , on a plastic film surface when an enclosed mass of air cools to a temperature below its dew point . the extent of the phenomenon depends on the actual temperature and relative humidity of the enclosed air mass , as well as the temperature of the plastic film . examples of the problems caused by this phenomenon include : fogging of food packaging in chiller cabinets and condensation within greenhouse complexes . food packaging needs to present its contents hygienically and aesthetically . fogging reduces a consumer &# 39 ; s ability to see the product and will give an impression of lower quality . in some applications condensation of water within the packaging may lead to actual reduction in quality . in the agricultural sector , the undesirable effects of fogging include for example ; reduced total light transmission in greenhouses and water dripping that can lead to plant damage . further plant damage may be induced by the focussing effect of the water droplets , rather like an array of lenses concentrating solar energy on foliage . the end result of all these effects for food producers is a lower potential yield and reduced product quality . eye protection is also increasingly important in today &# 39 ; s industrial environment . best practices dictate that employees exposed to eye hazards such as airborne debris , fumes , or even excess moisture , must wear goggles , shields or safety glasses . unfortunately , these eye safety systems are often plagued with fogging . that fogging often causes the frustrated employee to stop wearing their eye protection thus exposing themselves to potential injury and the company to a lawsuit for workers compensation claims . when goggles , shields or safety glasses do not provide adequate fog and condensation protection , employees may spend valuable production time constantly clearing the fog from these lenses . protective eyewear is often available with glass , plastic and polycarbonate lenses . however none of these provide adequate fog protection . the use of the “ anti - fog ” surface treatment such as described in the present invention will be suitable on polycarbonate lenses and other plastic lenses like those found in high - end safety eyewear and will aid in keeping protective eyewear fog free and a visibility clear . while exemplary embodiments incorporating the principles of the present invention have been disclosed hereinabove , the present invention is not limited to the disclosed embodiments . instead , this application is intended to cover any variations , uses , or adaptations of the invention using its general principles . further , this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains and which fall within the limits of the appended claims . 1 . emma dorey , chemistry & amp ; 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