Pigments for electrophoretic displays

Abstract

A polysiloxane-substituted quinacridone pigment is produced by a quinacridone pigment with an epoxy-terminated polysiloxane under conditions effective to cause the epoxy group on the polysiloxane to react with, and bond the polysiloxane to, the quinacridone pigment. The quinacridone pigment thus produced has the polysiloxane grouping bonded to one of the quinacridone nitrogen atoms via a hydrocarbon linking group, which bears a hydroxyl group on a carbon atom α or β to the quinacridone nitrogen atom. These quinacridone pigments are useful in electrophoretic displays.

Claims

1. A process for producing a quinacridone pigment having a polysiloxane-substituted quinacridone on the pigment surface, which process comprises adding an epoxy-terminated polysiloxane into a dispersion of quinacridone pigment in an organic solvent causing the epoxy group of the epoxy-terminated polysiloxane to react with a nitrogen atom of the quinacridone pigment forming the polysiloxane-substituted quinacridone of the formula ##STR00005## where L is a hydrocarbon linking group or a 3-alkoxypropyl linking group, Sil is a polysiloxane grouping and the broken line indicates that the hydroxyl substituent is attached to a carbon atom β to the quinacridone nitrogen atom, wherein R is hydrogen, C.sub.1-C.sub.3 alkyl group, or a halogen.

2. The process of claim 1 wherein the process for producing the quinacridone pigment involves a single reaction step.

3. The process of claim 1 wherein the polysiloxane is a polydialkylsiloxane.

4. The process of claim 1 wherein the polysiloxane has a molecular weight in the range of about 3,000 to about 30,000.

5. The process of claim 1 wherein the epoxy group of the polysiloxane forms part of an epoxyalkyl ether grouping or an epoxycycloalkyl grouping.

6. The process of claim 1 wherein the polysiloxane is of the formula: ##STR00006## wherein n is integer.

7. The process of claim 1 wherein the polysiloxane is of the formula: ##STR00007## wherein n and m are integers.

8. The process of claim 1 wherein the quinacridone pigment used is of the formula: ##STR00008## wherein each R independently is a hydrogen, C.sub.1-C.sub.3 alkyl group, or a halogen.

9. The process of claim 8 wherein both R groups are methyl groups.

10. An electrophoretic medium comprising particles of a pigment, prepared by a process according to claim 1, dispersed in a fluid.

11. The electrophoretic medium of claim 10 wherein the fluid comprises a hydrocarbon.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIGS. 1-5 of the accompanying drawings are color maps of the a*b* plane (in the conventional L*a*b* color space) showing the colors obtainable from various full color electrophoretic media of the present invention and similar prior art media, as described in the Examples below.

DETAILED DESCRIPTION

(2) As indicated above, the present invention provides a process for producing a polysiloxane-substituted quinacridone pigment, which process comprises reacting the quinacridone pigment with a epoxy-terminated polysiloxane under conditions effective to cause the epoxy group on the polysiloxane to react with, and bond the polysiloxane to, the quinacridone pigment, and the pigments so produced, and electrophoretic media and displays using these pigments.

(3) Also as noted above, multi-color electrophoretic displays comprising only a single layer of electrophoretic medium often depend for their operation upon close control of the interactions between the various types of particles. In particular, the electrophoretic medium described in the aforementioned US 2016/0085132 typically requires one particle (disclosed as the magenta particle) which has a polymer coating sufficient to enable the particle to be readily dispersed in the hydrocarbon fluids typically used in practical electrophoretic media but in which the polymeric layer is sufficiently sparse and the polymer chains themselves of sufficiently modest molecular weight to yield loosely flocculated dispersions in such hydrocarbon solvents in the absence of an added charge control agent (CCA). Such loosely flocculated hydrocarbon dispersions have a high viscosity with a consistency resembling that of tomato bisque. If one attempts to synthesize such pigments via prior art processes involving first attaching a polymerizable or polymerization-initiating group to the pigment particle and then effecting polymerization at the site of the polymerizable or polymerization-initiating group, it may be difficult to provide sufficiently accurate control of the molecular weights of the polymer chains so produced and/or the spread of molecular weights among polymer chains may be too large, with adverse effects on the properties of the polymer-coated pigment, or excessively variation between lots of the pigment. By attaching a pre-formed polymer chain directly to the pigment in a single step, the present invention allows very close control of the molecular weights of the polymer chains to provide consistent electro-optic properties and reduced variation between pigment lots.

(4) The following Examples are now given, though by way of illustration only, to show details of preferred reagents, conditions and techniques used in the process of the present invention, and the properties of the resultant pigments.

Example 1

(5) Ink Jet Magenta E02 (available from Clariant—1 part by weight) was added to ethyl acetate (approximately 7.8 parts by weight) and the resultant pigment dispersion was mixed under high shear and transferred to a 250 mL round bottom flask. Mono-(2,3-expoxy)propylether terminated polydimethylsiloxane, asymmetric (Gelest MCR-E21 molecular weight approximately 5000-about 1 part by weight) was added to the flask and the resultant mixture was allowed to react overnight under nitrogen at 46° C. The polymer-coated pigment was then removed from the flask, and washed and centrifuged several times to yield the final product.

(6) The resultant pigment was dispersed in Isopar (Registered Trade Mark) G hydrocarbon fluid to produce a 15.8 percent w/v dispersion. This dispersion was diluted with additional Isopar G and 50 percent by weight (based on the weight of the pigment) of Solsperse (Registered Trade Mark) 19K charge control agent was added to produce a dispersion containing 5 percent by weight solids. The zeta potential of this dispersion was measured in a standard test cell as +21 mV; in contrast, a prior art magenta pigment produced as described in the aforementioned US 2016/0085132 using the conventional two-step process as measured as approximately +40-50 mV under the same conditions.

Example 2

(7) Ink Jet Magenta E02 (1 part by weight) was added to ethyl acetate (approximately 7 parts by weight) and the resultant pigment dispersion was mixed under high shear and transferred to a 250 mL round bottom flask. [2-3% (epoxycyclohexylethyl)methylsiloxane]-dimethylsiloxane copolymer (Gelest ECMS-227 molecular weight approximately 18000-20000—about 1 part by weight) was added to the flask and the resultant mixture was allowed to react overnight under nitrogen at 46° C. The polymer-coated pigment was then removed from the flask, and washed and centrifuged several times to yield the final product.

(8) The resultant pigment was dispersed in Isopar G hydrocarbon fluid to produce a 15 percent w/v dispersion. This dispersion was diluted with additional Isopar G and 50 percent by weight (based on the weight of the pigment) of Solsperse 19K charge control agent was added to produce a dispersion containing 5 percent by weight solids. The zeta potential of this dispersion was measured in a standard test cell as +22 mV.

Example 3: Color Gamut Tests

(9) The pigment prepared in Example 1 above were formulated into multi-color electrophoretic media substantially as described in Example 13 of the aforementioned US 2016/0085132, using magenta pigments loadings of 3 and 3.5 percent by weight. A control medium was prepared using the prior art pigment used in Example 13. The media were driven at all eight colors as described in Example 13 and the average dsNAP and a maximum color gamut were calculated for each pigment. The results are shown in Table 1 below and are plotted in FIGS. 1-3.

(10) TABLE-US-00001 TABLE 1 Magenta Average Max Pigment R G B Y C M W K dSNAP Gamut Ex. 1, 3% 7 8 3 7 21 10 13 2 8.88 125551 Ex. 1, 3.5% 12 0 4 4 11 12 5 6 6.75 121560 Control 10 6 2 1 15 4 3 3 5.50 146623

(11) From Table 1 and FIGS. 1-3, it will be seen that both media containing a magenta pigment of the present invention gave a magenta saturation greater than that of the medium containing the prior art magenta pigment, and a comparable color gamut, even though the magenta pigment of Example 1 was used exactly as first prepared and no formulation optimization was performed.

(12) In a second series of experiments, the pigment prepared in Example 2 above was formulated into a multi-color electrophoretic medium substantially as described in Example 13 of the aforementioned US 2016/0085132, using a magenta pigment loading of 3 percent by weight. A control medium was prepared using the prior art pigment used in Example 13. The media were driven at all eight colors as described in Example 13 and the average dsNAP and a maximum color gamut were calculated for each pigment. The results are shown in Table 2 below and are plotted in FIGS. 4 and 5.

(13) TABLE-US-00002 TABLE 2 Magenta Average Max Pigment R G B Y C M W K dSNAP Gamut Control 6 10 1 8 11 7 6 3 6.50 104207 Ex. 2, 3% 13 10 5 9 17 8 11 1 9.25 115953

(14) From Table 2 and FIGS. 4 and 5, it will be seen that the media containing the magenta pigment of the present invention gave a magenta saturation greater than that of the medium containing the prior art magenta pigment, and a slightly larger color gamut, even though the magenta pigment of Example 2 was used exactly as first prepared and no formulation optimization was performed.

(15) From the foregoing, it will be seen that the present invention can provide a simple, single-step method of attaching polymer chains of varying molecular weights to quinacridone pigments. The resulting pigment sets allow fine tuning of the interaction energies of the magenta pigment with itself and with other pigments in multi-color single layer electrophoretic displays.

(16) It will be apparent to those skilled in the art that numerous changes and modifications can be made in the specific embodiments of the invention described above without departing from the scope of the invention. Accordingly, the whole of the foregoing description is to be interpreted in an illustrative and not in a limitative sense.