Electrophoretic fluids

Abstract

This invention relates to electrophoretic fluids, the use of these fluids for the preparation of an electrophoretic display device, and electrophoretic displays comprising such fluids.

Claims

1. An electrophoretic fluid comprising at least one solvent, at least one set of coloured particles, at least one highly absorbing dye, at least one set of white reflective particles, and at least one set of transparent particles, wherein the coloured particles and the white reflective particles have opposite electric charge signs and wherein the white reflective particles and the transparent particles have the same electric charge sign and wherein electrophoretic mobilities of the white reflective particles and the transparent particles differ at most by 50%, and wherein the white reflective particles, and the transparent particles comprise a polymeric shell adsorbed onto the particle wherein the polymeric shell consists of a random copolymer having monomer or macromonomer building blocks, and the random polymer comprises at least one hydrocarbon insoluble, charged or chargeable structural unit and at least one hydrocarbon soluble, stabilising structural unit; wherein the electrophoretic fluid comprises at least one highly absorbing dye according to Formula I, Formula II, Formula III, Formula IV or Formula V ##STR00032## wherein X and X are independently of one another H or an electron-withdrawing group; R.sub.1 and R.sub.2 are independently of one another groups are linear or branched, substituted or unsubstituted alkyl groups where one or more non-adjacent carbon atoms may be replaced by O, S and/or N; R.sub.3 and R.sub.4 are independently of one another groups are linear or branched, substituted or unsubstituted alkyl groups where one or more non-adjacent carbon atoms may be replaced by O, S and/or N; R5 is a methyl or methoxy group; and the dye comprises at least one electron-withdrawing group; ##STR00033## wherein R.sub.6 and R.sub.7 are independently of one another groups are linear or branched, substituted or unsubstituted alkyl groups where one or more non-adjacent carbon atoms may be replaced by O, S and/or N; ##STR00034## wherein X is an electron-withdrawing group; R.sub.8 is a methyl or methoxy group; R.sub.9 and R.sub.10 are independently of one another groups are linear or branched, substituted or unsubstituted alkyl groups where one or more non-adjacent carbon atoms may be replaced by O, S and/or N; ##STR00035## wherein R.sub.12 and R.sub.13 are independently of one another groups are linear or branched, substituted or unsubstituted alkyl groups where one or more non-adjacent carbon atoms may be replaced by O, S and/or N; R.sub.11 is an alkyl or alkoxy group with at least 3 carbon atoms; ##STR00036## wherein R.sub.14 and R.sub.15 are independently of one another groups are linear or branched, substituted or unsubstituted C8-C20 alkyl groups where one or more non-adjacent carbon atoms may be replaced by O, S and/or N; ##STR00037## wherein X is an electron-withdrawing group; R.sub.16 and R.sub.17 are independently of one another groups are linear or branched, substituted or unsubstituted alkyl groups where one or more non-adjacent carbon atoms may be replaced by O, S and/or N; R.sub.18 is NHCOR with R=linear or branched C1-C10 alkyl groups.

2. The electrophoretic fluid according to claim 1, wherein the electrophoretic fluid comprises the highly absorbing dye, wherein the coloured particles are black particles, a set of white reflective particles, and a set of transparent particles.

3. The electrophoretic fluid according to claim 1, wherein the electrophoretic mobilities of the white reflective particles and the transparent particles differ at most by 5%.

4. The electrophoretic fluid according to claim 1, wherein the dye or a dye mixture has an absorbance of at least 0.3 a.u. in a cell thickness of 50 microns.

5. The electrophoretic fluid according to claim 1, wherein the electrophoretic fluid comprises silica particles or polytetrafluoroethylene particles as transparent particles.

6. The electrophoretic fluid according to claim 1, wherein the least one set of white reflective particles is selected from the group consisting of titanium dioxide in the rutil, anatase, or amorphous modification, surface coated titanium dioxide, titanium dioxide based particles, and white polymer particles.

7. The electrophoretic fluid according to claim 1, wherein the coloured particles are black particles and are selected from the group consisting of carbon black, surface coated carbon black, carbon black based particles, and black polymer particles.

8. The electrophoretic fluid according to claim 1, wherein the white reflective particles, and the transparent particles comprise a polymeric shell adsorbed onto the particle wherein the polymeric shell consists of a random copolymer selected from random copolymers comprising mono-terminated polydimethylsiloxan methacrylate, (2,3-epoxypropyl)-methacrylat, and 2-tert-butylaminoethylmethacrylate or graft copolymers comprising polystearate methacrylate, (2,3-epoxypropyl)-methacrylat, and 2-tert-butylaminoethylmethacrylate or random copolymers comprising dodecylmethacrylate, and (2-(methylacryloyloxy) ethyltrimethyl ammonium methylsulfate.

9. The electrophoretic fluid according to claim 1, wherein the solvent comprises at least one non-polar solvent having a dielectric constant <10, volume resistivity about 10.sup.15 ohm-cm, viscosity <5 cst, and a boiling point >80 C.

10. The electrophoretic fluid according to claim 1, wherein the electrophoretic fluid further comprises at least one surfactant.

11. A method for the preparation of a mono, bi or polychromal electrophoretic device comprising utilizing the electrophoretic fluids according to claim 1.

12. A method comprising displaying an image with an electrophoretic fluid according to claim 1.

13. An electrophoretic display device comprising an electrophoretic fluid according to claim 1.

14. The Electrophoretic display device according to claim 13, wherein the electrophoretic fluid is applied by a technique selected from inkjet printing, slot die spraying, nozzle spraying, and flexographic printing, or any other contact or contactless printing or deposition technique.

Description

EXAMPLES

(1) The characterisation of the formulations is performed using a Malvern NanoZS particle analyser unless otherwise stated. This instrument measures the size of particles in dispersion and the zeta potential of an electrophoretic fluid. The Zeta potential (ZP) is derived from the real-time measurement of the electrophoretic mobility and thus is an indicator of the suitability of the fluid for use in electrophoretic applications.

(2) All chemicals are purchased from Sigma-Aldrich. All chemicals are purchased at the highest grade possible and are used without further purification unless otherwise stated.

(3) The following abbreviations are used:

(4) IMS industrial methylated spirit;

(5) NMP N-Methylpyrrolidone

(6) THF Tetrahydrofuran

(7) DCM Dichloromethane

(8) Mp melting point

(9) Colour particles in all examples are synthesised as exemplified in WO 2012/019704.

(10) White particles are synthesised as exemplified in the earlier patent application PCT/EP2013/000933.

(11) Black particles are synthesised as exemplified in WO 2013/079146.

(12) The characterisation of the formulations is performed using an Xrite Color i5 spectrophotometer to measure the colour coordinates of the extreme states.

(13) The absorbance of the dyes is measured using a Hitachi U3310 UV-vis spectrophotometer. All dye samples are measured at the concentration used in the examples, with no particles present, in glass cells with a 50 micron spacing.

Example 1: Dye 7: (E)-N,N-dibutyl-4-((4-butylphenyl)diazenyl)aniline

(14) ##STR00030##

(15) 4-Butylaniline (3.0 g, 20 mmol) is dissolved in 0.1N HCl (100 ml) and cooled to <5 C. by adding ice. 2N sodium nitrite solution is added dropwise at 5-10 C. until the solution no longer tested positive to Ehrlich's reagent and the excess nitrous acid is destroyed by adding sulfamic acid. N,N-Dibutylaniline (4.5 g, 22 mmol) is dissolved in a 50/50 mixture of pyridine/water (100 ml), ice (50 g) is added and the diazonium salt solution poured in. After stirring overnight, the resultant oil is extracted into hexane, dried (Na.sub.2SO.sub.4) and evaporated. The red oil is dissolved in a minimum volume of hexane, applied to silica gel and eluted with an increasing gradient of dichloromethane (30-50%) in hexane. The fractions containing pure yellow dye are combined and evaporated to an orange oil (6.0 g, 82%), .sub.max (hexane) 407 nm (38,000), FWHM 68 nm; .sup.1H NMR (300 MHz, CDCl.sub.3) 0.92 (3H, t, J 8.5), 0.96 (6H, t, J 8.5), 1.38 (6H, m), 1.64 (6H, m), 2.66 (2H, m), 3.36 (4H, m), 6.68 (2H, dm, J 9.0), 7.26 (2H, dm, J 8.5), 7.74 (2H, dm, J 8.5), 7.82 (2H, dm, J 9.0).

Example 2: Preparation of a Black Polymerisable Dye

(16) Prepared by a 7 step procedure according to Example 3 of WO 2013/079146 as detailed below:

(17) ##STR00031##

Step 1: 1,4-Bis(2-ethylhexyloxy)benzene

(18) Hydroquinone (37.9 g, 0.344 mol) is suspended in IMS (310 ml) and 1-bromo-2-ethylhexane (132.7 g, 0.687 mol) is added. A solution of KOH (49.9 g, 0.89 mol) in IMS (250 ml) is added slowly over 1 minute. The mixture is heated at reflux whilst monitoring reaction progress by HPLC. After 16 hours, further 1-bromo-2-ethylhexane (53.1 g, 0.27 mol) and solid KOH (20.0 g, 0.36 mol) are added then heated for 2 hours at reflux. The reaction mixture is allowed to cool, is poured into water (1.5 L) and extracted with toluene (500 ml). The organic layer is dried over MgSO.sub.4 then evaporated to yield a pale yellow oil. The oil is flashed through silica gel, eluting with 50/50 dichloromethane/hexane to give two product fractions. The initial fraction (35.3 g) co-eluted with 2-ethylhexan-1-ol by-product. The second fraction is evaporated to give pure 1,4-bis(2-ethylhexyloxy)benzene as a pale yellow oil (48.4 g, 42%). The initial fraction is further purified by bulb to bulb distillation to give further pure 1,4-bis(2-ethylhexyloxy)benzene as a pale yellow oil (25.3 g, 22%).

Step 2: 1,4-Bis(2-ethylhexyloxy)-2-nitrobenzene

(19) 1,4-Bis(2-ethylhexyloxy)benzene (50.2 g, 0.150 mol) is dissolved in chloroform (150 ml) and cooled to 0 C. Nitric acid (70%, 17.0 g, 0.190 mol) is added dropwise at 0-3 C. and the reaction stirred whilst monitoring progress by HPLC. After 60 minutes, water (50 ml) is added and the organic layer separated, dried (MgSO.sub.4) and evaporated to give the title compound as a yellow oil (56.9 g, 100%). The material is used without further purification.

Step 3: 2,5-Bis(2-ethylhexyloxy)aniline

(20) 1,4-Bis(2-ethylhexyloxy)-2-nitrobenzene (11.4 g, 0.03 mol) is dissolved in 2-propanol (100 ml) and degassed under vacuum, purging to nitrogen. 10% (w/w) Pd/C (0.52 g) is added and the mixture heated to 80 C. Water (10 ml) is added, followed by solid ammonium formate (18.9 g, 0.3 mol). After a further 1 hour at 80 C., the reaction mixture is allowed to cool then filtered to remove catalyst, to give a colourless solution which darkened rapidly on standing. The material is used immediately as an isopropanol solution (quant.).

Step 4: 4-((2,4-Dinitrophenyl)diazenyl)-2,5-bis(2-ethylhexyloxy)aniline

(21) 2,4-Dinitroaniline (3.7 g, 0.02 mol) is suspended in a mixture of acetic acid (20 ml) and propionic acid (10 ml) and cooled to 3 C. 40% (w/w) nitrosyl sulfuric acid in sulfuric acid (6.4 g, 0.02 mol) is added dropwise and stirring continued for 30 minutes to give a pale yellow solution. Crude 2,5-bis(2-ethylhexyloxy)aniline (0.02 mol) solution is diluted with IMS (200 ml) and 10% sulfamic acid solution (20 ml) added, followed by ice (200 g). The above pale yellow diazonium salt solution is slowly added with stirring and a dark oil rapidly separated. The mixture is stirred overnight and the water is decanted off. The crude product (8.3 g) is dissolved in 25/75 dichloromethane/hexane and purified over silica gel, the required product eluting with 50/50 hexane/dichloromethane. Evaporation and trituration with methanol gave 4-((2,4-dinitrophenyl)diazenyl)-2,5-bis(2-ethylhexyloxy)aniline as a violet-blue crystalline solid (4.2 g, 39%).

Step 5: 2,2-(4-((E)-(4-((E)-(2,4-Dinitrophenyl)diazenyl)-2,5-bis(2-ethylhexyloxy)phenyl)diazenyl)-3-methylphenylazanediyl)diethanol

(22) 4-((2,4-Dinitrophenyl)diazenyl)-2,5-bis(2-ethylhexyloxy)aniline (0.54 g, 1 mmol) is dissolved in NMP (10 ml) and to this is added 40% (w/w) nitrosyl sulfuric acid in sulfuric acid (0.38 g, 1.2 mmol). After 30 minutes, the mixture is added to a solution of 2,2-(m-tolylazanediyl)diethanol (0.20 g, 1 mmol) and sulfamic acid (0.5 g) in IMS (100 ml). A dark oily solid separates immediately. After stirring overnight, the aqueous supernatant is decanted off, the oily solid washed with further water, then dried at 40 C. The pure title compound is acquired as a blue-black solid after multiple purifications over silica gel, eluting with dichloromethane containing an increasing concentration of ethyl acetate (0.54 g, 72%).

Step 6: 2,2-(4-((E)-(4-((E)-(2,4-dinitrophenyl)diazenyl)-2,5-bis(2-ethylhexyloxy)phenyl)diazenyl)-3-methylphenylazanediyl)bis(ethane-2,1-diyl) bis(3-chloropropanoate)

(23) 2,2-(4-((E)-(4-((E)-(2,4-Dinitrophenyl)diazenyl)-2,5-bis(2-ethylhexyloxy)phenyl)diazenyl)-3-methylphenylazanediyl)diethanol (3.5 g, 5 mmol) is dissolved in dichloromethane (50 ml) and sodium bicarbonate (12.6 g, 0.15 mol) is added with stirring to suspend. 3-Chloropropionyl chloride (1.9 g, 15 mmol) is added and the mixture heated at 40 C. (bath temp.) overnight. The inorganics are filtered off, the dichloromethane is evaporated and the product solidified by adding IMS. A 2.7 g sample of crude product is taken through directly to the next step without further purification. A 1 g sample of material is recrystallised from IMS to obtain a pure sample as a violet/black crystalline solid; m.p 123-125 C., .sub.max (EtOAc) 573 nm (40,000), half bandwidth 160 nm, 353 nm (13,500).

Step 7: 2,2-(4-((E)-(4-((E)-(2,4-dinitrophenyl)diazenyl)-2,6-bis(2-ethylhexyloxy)phenyl)diazenyl)-3-methylphenylazanediyl)bis(ethane-2,1-diyl) diacrylate

(24) Crude 2,2-(4-((E)-(4-((E)-(2,4-dinitrophenyl)diazenyl)-2,5-bis(2-ethylhexyloxy)phenyl)diazenyl)-3-methylphenylazanediyl)bis(ethane-2,1-diyl) bis(3-chloropropanoate) (2.7 g, 2.9 mmol) is dissolved in dichloromethane (50 ml) and triethylamine (0.9 g, 8.7 mmol) is added. The mixture is heated at 30 C. (bath temp.) overnight and the product precipitated by adding IMS. The solid is recrystallised from hot IMS and the title compound is isolated as a violet/black powder; m.p 128-130 C., .sub.max (EtOAc) 574 nm (40,000), half bandwidth 160 nm, 354 nm (13,500).

Example 3: Polystearate Methacrylate (PSMA)

(25) 967.5 g of 12-hydroxystearic acid (TCl, H0308) are melted at 115 C. for 2 hours in a pre-weighed 2 liter 3-neck round bottom flask fitted with a thermometer, stopper, vacuum adaptor, magnetic stirrer, and heating mantle. 2.23 g Methane sulphonic acid (Aldrich) is added and the temperature adjusted to 105 C. Vacuum (65 mbar at the beginning and 20 mbar at the end of the reaction) is applied to extract water. The progress of the reaction is monitored in the .sup.1H NMR spectrum by following the decrease of the signal strength at 3.6 ppm compared to the 0.9 ppm resonance. The reaction is stopped once 99% conversion is reached.

(26) To 384.0 g of the resulting product, 384.0 g of xylene (Merck, 108685), 0.36 g of N,N-dimethyldodecylamine (Aldrich, 384386), 0.45 g of 4-tert-butylpyrocatechol (Merck, 801987) and 48.5 g of glycidyl methacrylate (Merck, 800609) are added. The reaction is continued at 140 C. under a nitrogen atmosphere. The progress of the reaction is monitored by determining the acid value by titration. The reaction is complete once an acid value of 0.0003 is reached. Titration is performed using a 0.05 M KOH in ethanol solution. Samples of approx. 0.5 g are removed from the reaction, diluted with toluene and titrated against phenolphthalein. The reaction product is diluted with xylene to obtain a polymer solution with a concentration of 50.0%.

Example 4: Charge Selective Dispersant

(27) 180 g of n-butyl acetate (Merck, 101974) are pre-heated to 85 C. (temperature at the heating block) in a 500 ml 3-neck flask equipped with reflux condenser, nitrogen supply, and septum. 38.4 g of polystearate methacrylate (Example 3; 52.2% solid dissolved in xylene), 2.0 g of (2,3-epoxypropyl)-methacrylate (Merck, 800609), 18.0 g of 2-tert-butylaminoethyl-methacrylate (Aldrich, 444332), and 0.48 g Vazo 67 (DuPont) are combined and added over a period of 3 hours using a dripping funnel. After addition of the reactants, an additional 0.48 g of Vazo 67 is added and the reaction is allowed to continue for 2 h. A polymer solution with a solid content of 15.2% is obtained.

Example 5: Modified TiO2 Pigment

(28) 13.2 g of the resulting polymer solution of Example 3, 10.0 g of TiO.sub.2 particles (DuPont, Ti-Pure R960), and 100.0 g dodecane (Merck, 820543) are combined in a plastic bottle and subjected to ultrasound for 3 min (Branson Sonifier B15, Standard horn and microtip, 150 W), while the reaction mixture is cooled by an ice bath. The dispersion is transferred to a 200 mL round bottom flask, 0.2 g diethanolamine (Merck, 116205) is added, and the mixture is reacted at 120 C. for 5 hours. The resulting dispersion is filtered through a 50 micron cloth (SEFAR NITEX 03-50/1). Afterwards, the particles are deposited (benchtop centrifuge, RCF=3000, 20 min) and redispersed in fresh dodecane thrice. The resulting dispersion has a solid content of 36.1%.

Example 6: Modified Monosphere Particles

(29) 10 g of freeze-dried, monodisperse SiO.sub.2 particles (Merck, Monosphere 250) with a diameter of 250 nm are combined with 6.6 g of the polymer solution of Example 2, and 50 ml of dodecane. The mixture is subjected to ultrasound for 3 min (Branson Sonifier B15, Standard horn and microtip) at 150 W. 0.1 g diethanolamine is added and the dispersion heated for 5 h at 120 C. A nearly transparent, blue translucent dispersion is obtained.

Example 7: Preparation of Black Polymer Particles

(30) Black polymer particles are prepared analogously to Example 6 of WO 2013/079146:

(31) NAD stabiliser 30% by weight in dodecane is obtained from ICI Ltd. precipitated in cold methanol, dried and dissolved in a 50:50 mixture of ethyl acetate (Aldrich) and butyl acetate (Aldrich). All materials other than dyes are commercially available.

(32) Methyl methacrylate (20.58 g), NAD stabiliser (3.50 g) and methacrylic acid (0.42 ml) are weighed out into a 100 ml 3-necked flask equipped with a condenser, nitrogen flow, and an overhead stirrer. 1.029 g (5 weight %) of the black polymerisable dye of Example 2 is added and stirred for 1 minute to facilitate dissolution of the dye. Dodecane (25.20 g) is added to the reaction flask, followed by 1-octanethiol (0.125 ml). The mixture is heated with stirring at 300 rpm, once the temperature in the flask is at 75 C., Vazo 67 (0.20 g) is added and the reaction is stirred for 2 hours.

(33) The resulting solution is filtered through 50 micron cloth to remove small lumps. The particles are cleaned using a centrifuge. Centrifugations are carried out at 10 000 rpm for 40 minutes each, replacing the supernatant with dodecane; this is repeated until the supernatant is colourless. Average particle size is measured by SEM and image analysis: 547 nm.

Example 8: Modified PTFE Particles

(34) 10 g of PTFE particles (Aldrich, 430935) with a diameter of 1000 nm are combined with 3.55 g of the resulting polymer solution of Example 8, and 40 ml Dodecane (Merck, 820543) are combined in a plastic bottle and subjected to ultrasound for 3 min (Branson Sonifier B15, Standard horn and microtip, 150 W), while the reaction mixture is cooled by an ice bath. The dispersion is transferred to a 100 mL round bottom flask, and the mixture is heated to 120 C. for 4 hours. Remaining coagulates are allowed to sediment and separated from the dispersion. Afterwards, the particles are deposited (benchtop centrifuge, RCF=3000, 20 min) and redispersed in fresh dodecane thrice and filtered through a 50 micron cloth (SEFAR NITEX 03-50/1). The resulting dispersion has a solid content of 41.2%.

Example 9: Electrophoretic Dispersions

(35) Electrophoretic dispersions with white, transparent, and black particles according to Examples 5, 6, and 7 are prepared by vortex mixing of the components in dodecane and then roller mixing of the dispersion. A saturated solution of Dye 7 of Example 1 is added to 1.0 g of the dispersions and vortex mixed. The formulations are roller mixed for 24 hours and then the colour of the saturated colour state is measured using an Xrite Color i5 spectrophotometer in reflection mode, specular excluded, d65 illumination. Amounts of the components and the results are shown in Table 5.

(36) xy colour coordinates are measured at +22V and 22V using the Xrite Color i5 spectrophotometer with integrating sphere, measured in cells of 50 micron thickness with no insulating layers present. Colour State Reflectivity (CSR %) is measured at 22V using the Autronics DMS-301 display measurement system. Ton corresponds to the time in ms taken for the dark state to switch to the bright state (from 10% to 90% of reference values for the extreme states). Toff corresponds to the time in ms taken for the bright state to switch to the dark state (from 90% to 10% of reference values for the extreme states).

(37) Increase in CSR % column and in x,y colour coordinate shows that the colour is more saturated and bright. (yellow is to the top right of the colour space, so high x and high y=improved saturation.

(38) Data also show that increasing silica content slows down response time (trade off).

FIGURES

(39) FIG. 1 shows the effect of silica on Yellow State R %

(40) FIG. 2 shows the effect of silica on Yellow State x,y coordinate

(41) TABLE-US-00005 TABLE 5 white transparent Black Yellow CSR % Ton Toff particles of particles of particles of alkyl aryl dye of x y x y CSR % at 22 V (t90- (t90- Ex. 5 Ex. 6 Ex. 7 AOT sulfonate Ex. 1 (+22 V) (+22 V) (22 V) (22 V) at 22 V (SWC) t10) t10) 14.99 0.00 4.99 2.52 2.01 4.99 0.3505 0.4019 0.4942 0.4743 19.17 18.75 102 153 14.99 1.01 5.00 2.50 1.99 4.92 0.3556 0.4075 0.5025 0.4675 21.76 21.43 105 176 14.73 1.95 4.93 2.79 1.97 5.33 0.3612 0.4131 0.5044 0.4677 22.58 21.18 104 157 15.01 4.97 5.02 2.45 2.00 5.03 0.3608 0.4126 0.5093 0.4649 24.78 22.55 162 206 14.89 9.94 5.05 2.54 2.00 5.17 0.3703 0.4243 0.5154 0.4643 26.95 24.18 273 274 14.79 14.68 4.71 2.42 1.97 5.13 0.3829 0.4361 0.5091 0.4560 29.76 24.2 364 432