HK1244545B - Electrophoretic display fluid - Google Patents
Electrophoretic display fluid Download PDFInfo
- Publication number
- HK1244545B HK1244545B HK18103169.9A HK18103169A HK1244545B HK 1244545 B HK1244545 B HK 1244545B HK 18103169 A HK18103169 A HK 18103169A HK 1244545 B HK1244545 B HK 1244545B
- Authority
- HK
- Hong Kong
- Prior art keywords
- particles
- type
- types
- fluid
- charge
- Prior art date
Links
Description
发明领域Field of the Invention
本发明涉及一种电泳显示流体和使用这种显示流体的电泳装置。The present invention relates to an electrophoretic display fluid and an electrophoretic device using the same.
发明背景Background of the Invention
电泳显示器(EPD)是一种基于影响分散于介电溶剂中的带电颜料粒子的电泳现象的非辐射装置。EPD典型地包括一对间隔开的板状电极。电极板中的至少一个典型地在观察侧是透明的。由带电颜料粒子分散于其中的介电溶剂构成的电泳流体被封装在两个电极板之间。An electrophoretic display (EPD) is a non-radiative device based on the electrophoretic phenomenon that affects charged pigment particles dispersed in a dielectric solvent. An EPD typically comprises a pair of spaced-apart plate-shaped electrodes. At least one of the electrode plates is typically transparent on the viewing side. An electrophoretic fluid, consisting of a dielectric solvent in which the charged pigment particles are dispersed, is enclosed between the two electrode plates.
电泳流体可包括一种或多种类型的带电粒子。对于彩色电泳显示装置,流体通常包括至少三种类型的带电粒子。其中有白色粒子、黑色粒子和非白色和非黑色粒子。对于非白色和非黑色粒子,有机颜料由于其优异的着色强度而经常被使用。Electrophoretic fluids can include one or more types of charged particles. For color electrophoretic display devices, the fluid typically includes at least three types of charged particles. These include white particles, black particles, and non-white and non-black particles. For non-white and non-black particles, organic pigments are often used due to their excellent tinting strength.
但实际上,仅有几种类型的表面改性技术可用于制备有机颜料粒子,以使它们在电泳显示器中起作用。如果具有不同颜色的有机颜料粒子在流体中共存并且它们具有相同的表面化学,则这些粒子在给定的驱动电压下可能难以分离。这是由于以下事实:因为这些粒子具有相同的表面化学,所以难以将它们制备成具有期望的电荷极性和不同水平的电荷电位。In practice, however, only a few types of surface modification techniques are available for preparing organic pigment particles to function in electrophoretic displays. If organic pigment particles of different colors coexist in a fluid and have the same surface chemistry, these particles can be difficult to separate at a given drive voltage. This is due to the fact that because these particles have the same surface chemistry, it is difficult to prepare them to have the desired charge polarity and different levels of charge potential.
而且,如果在流体中使用电荷控制剂(多种电荷控制剂),则具有相同的表面化学的不同着色的有机颜料粒子将争夺相同的电荷控制剂,导致在驱动期间电荷不稳定。所有这些因素都可能导致显示装置的差的色彩表现,诸如存在着色和差的颜色对比度。Furthermore, if a charge control agent (or multiple charge control agents) is used in the fluid, differently colored organic pigment particles with the same surface chemistry will compete for the same charge control agent, resulting in charge instability during driving. All of these factors can lead to poor color performance of the display device, such as coloration and poor color contrast.
发明详述Detailed Description of the Invention
在本发明中,使用无机彩色颜料代替包括两种或更多种类型的非白色和非黑色粒子的电泳流体中的至少一种有机彩色颜料。In the present invention, an inorganic color pigment is used instead of at least one organic color pigment in an electrophoretic fluid including two or more types of non-white and non-black particles.
本发明的第一个方面涉及一种包括分散在溶剂或溶剂混合物中的至少两种类型的带电粒子的电泳流体,其中:A first aspect of the present invention relates to an electrophoretic fluid comprising at least two types of charged particles dispersed in a solvent or a solvent mixture, wherein:
(i)一种类型的粒子为非白色和非黑色并由无机颜料形成,(i) one type of particles is non-white and non-black and is formed from an inorganic pigment,
(ii)另一种类型的粒子为非白色和非黑色并由有机颜料形成,以及(ii) another type of particle is non-white and non-black and is formed from an organic pigment, and
两种类型的粒子具有不同的颜色并带有相同的电荷极性。The two types of particles have different colors and carry the same charge polarity.
在一个实施方案中,流体包括一种另外类型的不同着色的粒子(即总共三种类型)。在一个实施方案中,流体包括两种另外类型的不同着色的粒子(即总共四种类型)。在一个实施方案中,流体包括三种另外类型的不同着色的粒子(即总共五种类型)。在一个实施方案中,流体包括多于五种类型的不同着色的粒子。In one embodiment, the fluid comprises one additional type of differently colored particles (i.e., three types in total). In one embodiment, the fluid comprises two additional types of differently colored particles (i.e., four types in total). In one embodiment, the fluid comprises three additional types of differently colored particles (i.e., five types in total). In one embodiment, the fluid comprises more than five types of differently colored particles.
在一个实施方案中,两种类型的粒子(i)和(ii)均带正电荷。在一个实施方案中,两种类型的粒子具有不同类型的表面化学。In one embodiment, both types of particles (i) and (ii) are positively charged. In one embodiment, the two types of particles have different types of surface chemistries.
在一个实施方案中,(i)类型的粒子比(ii)类型的粒子携带更高的电荷。In one embodiment, particles of type (i) carry a higher charge than particles of type (ii).
在一个实施方案中,流体包括另外类型的相同地带电的粒子,其为黑色或白色。在该实施方案中,所述三种类型的粒子带正电。在一个实施方案中,所述另外类型的相同地带电的粒子为黑色。在另一个实施方案中,所述三种类型的粒子携带不同水平的电荷电位。在又一个实施方案中,(i)类型粒子的量和(ii)类型粒子的量逐步小于所述另外类型的相同地带电的粒子的量。换句话说,所述另外类型的相同地带电的粒子携带最高的电荷电位;(ii)类型的粒子携带最低的电荷电位;并且(i)类型的粒子的电荷量介于所述另外类型的相同地带电的粒子的电荷量与(ii)类型的粒子的电荷量之间。In one embodiment, the fluid includes additional types of identically charged particles that are black or white. In this embodiment, the three types of particles are positively charged. In one embodiment, the additional types of identically charged particles are black. In another embodiment, the three types of particles carry different levels of charge potential. In yet another embodiment, the amount of type (i) particles and the amount of type (ii) particles are progressively less than the amount of the additional types of identically charged particles. In other words, the additional types of identically charged particles carry the highest charge potential; the types of particles (ii) carry the lowest charge potential; and the charge of the types of particles (i) is between the charge of the additional types of identically charged particles and the charge of the types of particles (ii).
在一个实施方案中,流体还包括带相反电荷的其它类型的粒子。在一个实施方案中,其它类型的粒子带负电荷。In one embodiment, the fluid further comprises other types of particles having an opposite charge. In one embodiment, the other types of particles are negatively charged.
本发明的第二个方面涉及一种包括第一种类型的粒子、第二种类型的粒子、第三种类型的粒子、第四种类型的粒子和第五种类型的粒子的电泳流体,所述第一种、第二种、第三种、第四种和第五种类型的粒子全部都分散在溶剂或溶剂混合物中,其中:A second aspect of the present invention relates to an electrophoretic fluid comprising a first type of particles, a second type of particles, a third type of particles, a fourth type of particles, and a fifth type of particles, wherein the first, second, third, fourth, and fifth types of particles are all dispersed in a solvent or solvent mixture, wherein:
(a)所述五种类型的粒子具有彼此不同的颜色;(a) the five types of particles have colors different from each other;
(b)所述第一种、第二种和第三种类型的粒子携带相同的电荷极性,(b) the particles of the first, second and third types carry the same charge polarity,
(c)所述第二种类型的粒子为非白色和非黑色并由无机颜料形成,并且所述第三种类型的粒子为非白色和非黑色并由有机颜料形成;(c) the second type of particles are non-white and non-black and are formed of an inorganic pigment, and the third type of particles are non-white and non-black and are formed of an organic pigment;
(d)所述第四和第五种类型的粒子携带的电荷与第一种、第二种和第三种类型的粒子所携带的电荷相反。(d) The fourth and fifth types of particles carry charges opposite to the charges carried by the first, second and third types of particles.
在一个实施方案中,第一种、第二种和第三种类型的粒子带正电荷。在一个实施方案中,第一种类型的粒子是黑色的。在一个实施方案中,第二种类型和第三种类型的粒子具有比第一种类型的粒子逐步更小的量。换句话说,第一种类型的粒子带最高电荷,第三种类型的粒子带最低电荷,并且第二种类型的粒子的电荷量介于第一种和第三种类型的粒子的电荷量之间。In one embodiment, the first, second, and third types of particles are positively charged. In one embodiment, the first type of particles are black. In one embodiment, the second and third types of particles are present in progressively smaller amounts than the first type of particles. In other words, the first type of particles are the most highly charged, the third type of particles are the least highly charged, and the second type of particles have a charge intermediate between the first and third types of particles.
在一个实施方案中,第二种类型的粒子比第三种类型的粒子携带更高的电荷。In one embodiment, the second type of particles carries a higher charge than the third type of particles.
在一个实施方案中,第四种和第五种类型的粒子带负电荷。在一个实施方案中,第五种类型的粒子的量小于第四种类型的粒子的量。In one embodiment, the fourth and fifth types of particles are negatively charged. In one embodiment, the amount of the fifth type of particles is less than the amount of the fourth type of particles.
除了颜色之外,可能多种类型的粒子具有其它不同的光学特性,诸如光传输、反射率、发光(luminescence),或在旨在用于机器读取的显示器的情况下,在可见范围外的电磁波长的反射率变化的意义上的伪彩色。In addition to color, it is possible for the multiple types of particles to have other different optical properties, such as light transmission, reflectivity, luminescence, or, in the case of displays intended for machine reading, false color in the sense of varying reflectivity for electromagnetic wavelengths outside the visible range.
粒子的电荷电位可以根据ζ电位(zeta potential)测量。在一个实施方案中,ζ电位通过具有CSPU-100信号处理单元、ESA EN#Attn流通池(K:127)的Colloidal DynamicsAcoustoSizer IIM来确定。在测试前输入仪器常数,如样品中使用的溶剂的密度、溶剂的介电常数、溶剂中的声速、溶剂的粘度,所有这些常数都是在测试温度(25℃)下的常数。颜料样品分散在溶剂(通常是碳原子数小于12的烃流体)中,并按重量稀释至5-10%。该样品还含有电荷控制剂(Solsperse可得自Lubrizol Corporation,BerkshireHathaway公司;“Solsperse”是注册商标),电荷控制剂与粒子的重量比为1:10。确定稀释的样品的质量,然后将样品装载到流通池中以用于确定ζ电位。The charge potential of the particles can be measured according to the zeta potential. In one embodiment, the zeta potential is determined by a Colloidal Dynamics AcoustoSizer IIM with a CSPU-100 signal processing unit and an ESA EN#Attn flow cell (K:127). Instrument constants such as the density of the solvent used in the sample, the dielectric constant of the solvent, the speed of sound in the solvent, and the viscosity of the solvent are input before the test, all of which are constants at the test temperature (25°C). The pigment sample is dispersed in a solvent (usually a hydrocarbon fluid having a carbon atom number less than 12) and diluted to 5-10% by weight. The sample also contains a charge control agent (Solsperse available from Lubrizol Corporation, Berkshire Hathaway; "Solsperse" is a registered trademark) with a weight ratio of charge control agent to particles of 1:10. The mass of the diluted sample is determined and then the sample is loaded into the flow cell for determining the zeta potential.
对于非白色和非黑色有机颜料,它们可以包括但不限于CI颜料PR254、PR122、PR149、PG36、PG58、PG7、PB15:3、PY83、PY138、PY150、PY155或PY20。这些是在颜色索引手册“New Pigment Application Technology”(CMC Publishing Co.Ltd,1986)和“PrintingInk Technology”(CMC Publishing Co.,Ltd,1984)中描述的常用有机颜料。具体示例包括科莱恩公司的Hostaperm Red D3G 70-EDS、Hostaperm Pink E-EDS、PV Fast Red D3G、Hostaperm Red D3G 70、Hostaperm Blue B2G-EDS、Hostaperm Yellow H4G-EDS、F2G-EDS、Novoperm Yellow HR-70-EDS、Hostaperm Green GNX、BASF Irgazine Red L 3630、Cinquasia Red L 4100HD和Irgazin Red L 3660HD;太阳化学公司的酞菁蓝、酞菁绿、二芳基黄或二芳基AAOT黄。As for non-white and non-black organic pigments, they may include, but are not limited to, CI pigments PR254, PR122, PR149, PG36, PG58, PG7, PB15:3, PY83, PY138, PY150, PY155, or PY20. These are commonly used organic pigments described in the color index manuals "New Pigment Application Technology" (CMC Publishing Co. Ltd, 1986) and "Printing Ink Technology" (CMC Publishing Co., Ltd, 1984). Specific examples include Hostaperm Red D3G 70-EDS, Hostaperm Pink E-EDS, PV Fast Red D3G, Hostaperm Red D3G 70, Hostaperm Blue B2G-EDS, Hostaperm Yellow H4G-EDS, F2G-EDS, Novoperm Yellow HR-70-EDS, Hostaperm Green GNX, BASF Irgazine Red L 3630, Cinquasia Red L 4100HD, and Irgazin Red L 3660HD; and Sun Chemical's Phthalocyanine Blue, Phthalocyanine Green, Diaryl Yellow, or Diaryl AAOT Yellow.
对于非白色和非黑色无机颜料,它们可以包括但不限于通常通过高温煅烧工艺制备的混合金属氧化物颜料,诸如CI(比色指数)颜料蓝36或28(PB36或PB28)、CI颜料黄227或53、CI颜料绿50或26、CI颜料红102等。For non-white and non-black inorganic pigments, they may include but are not limited to mixed metal oxide pigments typically prepared by a high temperature calcination process, such as CI (Color Index) Pigment Blue 36 or 28 (PB36 or PB28), CI Pigment Yellow 227 or 53, CI Pigment Green 50 or 26, CI Pigment Red 102, etc.
颜料粒子分散于其中的溶剂的介电常数为约2至约30,优选为约2至约15,用于高粒子迁移率。合适的介电溶剂的示例包括烃类,诸如Isopar、十氢化萘(DECALIN)、5-亚乙基-2-降冰片烯、脂肪油、石蜡油;硅流体;芳香烃类,诸如甲苯、二甲苯、苯基二甲基乙烷、十二烷基苯和烷基萘;卤代溶剂,诸如全氟代萘烷、全氟甲苯、全氟二甲苯、二氯三氟甲苯、3,4,5-三氯三氟甲苯、氯五氟苯、二氯壬烷、五氯苯;以及诸如来自St.Paul MN的3M公司的FC-43、FC-70和FC-5060的全氟化溶剂,诸如来自美国波特兰俄勒冈州的TCI的聚(全氟环氧丙烷)的低分子量含卤素的聚合物,诸如来自新泽西的River Edge的Halocarbon ProductCorp.的卤烃油的聚(氯三氟乙烯),诸如来自Ausimont的Galden或来自特拉华州的DuPont的Krytox Oils和Greases K-Fluid Series的全氟聚烷基醚,来自Dow-corning的基于聚二甲基硅氧烷的硅油(DC-200)。The solvent in which the pigment particles are dispersed has a dielectric constant of about 2 to about 30, preferably about 2 to about 15 for high particle mobility. Examples of suitable dielectric solvents include hydrocarbons such as Isopar, decaline (DECALIN), 5-ethylidene-2-norbornene, fatty oils, paraffin oils; silicone fluids; aromatic hydrocarbons such as toluene, xylene, phenyldimethylethane, dodecylbenzene, and alkylnaphthalenes; halogenated solvents such as perfluorodecalin, perfluorotoluene, perfluoroxylene, dichlorobenzotrifluoride, 3,4,5-trichlorobenzotrifluoride, chloropentafluorobenzene, dichlorononane, pentachlorobenzene; and perfluorinated solvents such as FC-43, FC-70, and FC-5060 from 3M Company in St. Paul, MN, low molecular weight halogen-containing polymers such as poly(perfluoropropylene oxide) from TCI in Portland, Oregon, USA, poly(chlorotrifluoroethylene) such as halocarbon oils from Halocarbon Product Corp. in River Edge, New Jersey, Krytox Oils and Greases from Galden in Ausimont or DuPont in Delaware. Perfluoropolyalkyl ether of the K-Fluid Series, a polydimethylsiloxane-based silicone oil (DC-200) from Dow-corning.
粒子(有机和无机)可显示固有电荷,或者可以明确地使用电荷控制剂带电,或者当悬浮于溶剂或溶剂混合物中时可获得电荷。Particles (organic and inorganic) may exhibit an intrinsic charge, or may be explicitly charged using a charge control agent, or may acquire a charge when suspended in a solvent or solvent mixture.
合适的电荷控制剂是本领域熟知的;它们在本质上可以是聚合的或非聚合的,或者可以是离子或非离子的。电荷控制剂的示例可包括但不限于:Solsperse 17000(活性聚合物分散剂)、Solsperse 19000、Solsperse 9000(活性聚合物分散剂)、OLOA 11000(琥珀酰亚胺无灰分散剂)、Unithox 750(乙氧基化物)、Span 85(脱水山梨糖醇三油酸酯)、Petronate L(磺酸钠)、Alcolec LV30(大豆卵磷脂)、Petrostep B100(石油磺酸盐)、B70(磺酸钡)、Aerosol OT、聚异丁烯衍生物、聚(乙烯-共-丁烯)衍生物等。Suitable charge control agents are well known in the art; they can be polymeric or non-polymeric in nature, or ionic or non-ionic. Examples of charge control agents may include, but are not limited to: Solsperse 17000 (reactive polymeric dispersant), Solsperse 19000, Solsperse 9000 (reactive polymeric dispersant), OLOA 11000 (succinimide ashless dispersant), Unithox 750 (ethoxylate), Span 85 (sorbitan trioleate), Petronate L (sodium sulfonate), Alcolec LV30 (soy lecithin), Petrostep B100 (petroleum sulfonate), B70 (barium sulfonate), Aerosol OT, polyisobutylene derivatives, poly(ethylene-co-butylene) derivatives, and the like.
以下提供可用于改性本发明的粒子的表面的几种方法。Several methods that can be used to modify the surface of the particles of the present invention are provided below.
I.表面改性方法:I. Surface modification methods:
一种类型的表面改性方法是表面接枝。对于在表面上具有羟基(-OH)官能团的颜料,可以使用有机硅烷偶联剂与羟基官能团反应,由此具有可聚合官能团的分子可化学键合到颜料表面。然后将进行表面聚合以将聚合物接枝到颜料粒子的表面上。One type of surface modification method is surface grafting. For pigments with hydroxyl (-OH) functional groups on the surface, an organosilane coupling agent can be used to react with the hydroxyl functional groups, thereby chemically bonding molecules with polymerizable functional groups to the pigment surface. Surface polymerization is then performed to graft the polymer onto the surface of the pigment particles.
无机颜料通常通过这种方法,因为在金属氧化物表面上天生就存在羟基(-OH)官能团。但是,如果有机颜料具有羟基(-OH)官能团,则该方法也可适用于有机颜料。Inorganic pigments are usually treated by this method because of the inherent presence of hydroxyl (-OH) functional groups on the metal oxide surface. However, this method can also be applied to organic pigments if they have hydroxyl (-OH) functional groups.
美国专利No.6,822,782中描述了该类型的化学和方法,其内容作为整体通过引用并入本文。Chemistry and methods of this type are described in US Patent No. 6,822,782, the contents of which are incorporated herein by reference in their entirety.
I(a)自由基无规接枝聚合(RGP)方法I(a) Radical Random Graft Polymerization (RGP) Method
该方法更适用于无机颜料。其中,首先使粒子与具有官能团和可聚合基团的试剂反应,其中官能团能够与粒子表面反应并键合至粒子表面。官能团与粒子表面反应,使可聚合基团共价键合至粒子表面并自由参与随后的聚合反应。然后在有效引起粒子上的可聚合基团和单体(多种单体)或低聚物(多种低聚物)之间的反应的条件下,用一种或多种可聚合单体或低聚物处理携带可聚合基团的粒子;这样的条件通常包括聚合引发剂的存在,但在一些情况下聚合可以是热引发的,没有引发剂存在。This method is more suitable for inorganic pigments. Therein, the particles are first reacted with a reagent having a functional group and a polymerizable group, wherein the functional group is capable of reacting with and bonding to the particle surface. The functional group reacts with the particle surface, leaving the polymerizable group covalently bonded to the particle surface and free to participate in subsequent polymerization reactions. The particles carrying the polymerizable group are then treated with one or more polymerizable monomers or oligomers under conditions effective to induce a reaction between the polymerizable group on the particle and the monomer(s) or oligomer(s); such conditions typically include the presence of a polymerization initiator, but in some cases polymerization can be thermally initiated without the presence of an initiator.
聚合反应产生聚合物链,其包括至少一个来自之前附接到粒子上的可聚合基团的残基。如果在该工艺的第一阶段将多个可聚合基团附接到粒子,则这些可聚合基团中的两个或更多个可聚合基团的残基可以被合并到同一聚合物链中,因此该聚合物链将在两个或多个点处附接至粒子表面。The polymerization reaction produces a polymer chain that includes at least one residue from a polymerizable group previously attached to the particle. If multiple polymerizable groups are attached to the particle in the first stage of the process, the residues of two or more of these polymerizable groups can be incorporated into the same polymer chain, which will then be attached to the particle surface at two or more points.
据信存在多重附接的聚合物链对于稳定电泳流体中使用的粒子是特别有利的。聚合物链不完全覆盖粒子的表面。通过聚合物链对颜料粒子的表面的不完全覆盖在给粒子提供好的电泳性质方面是重要的。It is believed that the presence of multiple attached polymer chains is particularly advantageous for stabilizing particles used in electrophoretic fluids. The polymer chains do not completely cover the surface of the particles. Incomplete coverage of the surface of the pigment particles by the polymer chains is important in providing good electrophoretic properties to the particles.
I(b)离子无规接枝聚合(离子型RGP)方法I(b) Ionic Random Graft Polymerization (Ionic RGP) Method
可替换地,可聚合基团可以经由离子键附接到粒子。根据粒子的化学性质,在一些情况下,简单地使单体与粒子反应以形成所需的离子键是可能的。然而,在大多数情况下,将有必要用具有一个能够与粒子反应并键合至粒子的官能团和能够形成必需的离子键的第二官能团的双官能试剂预处理粒子。然后,使得到的粒子与具有可聚合基团和能够与第二官能团反应以形成期望的离子键的第三官能团的单体反应。然后如前所述进行RGP工艺的最终聚合步骤以制备产物。离子键形成反应通常是酸碱反应;例如,第二官能团可以是铵基,如烷基取代的铵基,而第三官能团可以是磺酸,反之亦然。Alternatively, the polymerizable group can be attached to the particle via an ionic bond. Depending on the chemical properties of the particle, in some cases, it is possible to simply react the monomer with the particle to form the desired ionic bond. However, in most cases, it will be necessary to pre-treat the particle with a bifunctional reagent having one functional group capable of reacting with and bonding to the particle and a second functional group capable of forming the necessary ionic bond. The resulting particle is then reacted with a monomer having a polymerizable group and a third functional group capable of reacting with the second functional group to form the desired ionic bond. The final polymerization step of the RGP process is then carried out as described above to prepare the product. The ionic bond forming reaction is typically an acid-base reaction; for example, the second functional group may be an ammonium group, such as an alkyl-substituted ammonium group, and the third functional group may be a sulfonic acid, or vice versa.
同样更适合用于无机颜料的离子-RGP工艺具有以下优点:最终的粒子中的一些离子键合的聚合物链可以分离并分散在电泳流体的悬浮液中,因此给带电粒子提供稳定化的抗衡离子。实际上,离子键合的聚合物用作粒子的稳定聚合物和电荷控制剂两者。The ion-RGP process, which is also more suitable for inorganic pigments, has the following advantages: some of the ionically bonded polymer chains in the final particles can separate and disperse in the suspension of the electrophoretic fluid, thus providing stabilizing counterions to the charged particles. In effect, the ionically bonded polymer acts as both a stabilizing polymer and a charge control agent for the particles.
I(c)原子转移自由基聚合(ATRP)方法I(c) Atom Transfer Radical Polymerization (ATRP) Method
进一步可替换地,可以首先将能够引发聚合的基团附接到颜料粒子和由该引发基团形成聚合物。引发基团可以通过共价或离子键以前述方式中的任何方式附接到聚合物表面。在该工艺的第一阶段,利用具有一个能够与粒子表面反应的基团和为原子转移自由基聚合(ATRP)提供引发位点的第二基团的双官能试剂处理粒子的表面。ATRP引发剂位点可以是例如苄基氯或其它卤素原子。然后用原子转移自由基可聚合单体(例如甲基丙烯酸甲酯)处理所得到的粒子以在粒子表面上形成聚合物。ATRP的优点是:可以通过冷却反应混合物停止与第一单体的聚合反应,用第二单体代替第一单体,然后通过升高反应混合物的温度重新开始反应,以使第二单体聚合到第一单体的之前形成的聚合物的端部。在引入第三单体的情况下,可以重复这些步骤。该工艺在粒子上形成两种(或多种)单体的嵌段共聚物。Alternatively, a group capable of initiating polymerization can first be attached to the pigment particles and a polymer can be formed by the initiating group. The initiating group can be attached to the polymer surface in any of the aforementioned ways by covalent or ionic bonds. In the first stage of the process, a bifunctional reagent having a group capable of reacting with the particle surface and a second group providing an initiation site for atom transfer radical polymerization (ATRP) is used to treat the surface of the particles. The ATRP initiator site can be, for example, benzyl chloride or other halogen atoms. The resulting particles are then treated with an atom transfer radical polymerizable monomer (e.g., methyl methacrylate) to form a polymer on the particle surface. The advantage of ATRP is that the polymerization reaction with the first monomer can be stopped by cooling the reaction mixture, the first monomer can be replaced by the second monomer, and then the reaction can be restarted by raising the temperature of the reaction mixture so that the second monomer is polymerized to the end of the polymer previously formed of the first monomer. When a third monomer is introduced, these steps can be repeated. The process forms a block copolymer of two (or more) monomers on the particles.
该方法不限于使用粒子上的ATRP引发位点,而且还包括使用其它类型的引发位点,例如离子或自由基引发位点。而且,上述双功能试剂不必是单一的单体试剂,而是本身可以是聚合的。The method is not limited to the use of ATRP initiation sites on the particles, but also includes the use of other types of initiation sites, such as ionic or free radical initiation sites. Furthermore, the above-mentioned bifunctional reagents need not be single monomeric reagents, but can themselves be polymeric.
ATRP方法同样更适合用于无机颜料。The ATRP method is also more suitable for inorganic pigments.
本部分中的方法可以包括多于一个阶段和/或多于一种类型的聚合。例如,除了使用含有至少一种包括为ATRP提供引发位点的基团的单体(例如,氯甲基苯乙烯)的单体混合物以外,粒子首先经受上述自由基聚合方法。因此,在粒子上形成含有ATRP引发位点的聚合物链。在自由基聚合结束后,然后使粒子经受ATRP,使得由ATRP引发位点形成聚合物侧链,从而产生具有通过RGP工艺形成的主链和通过ATRP形成的侧链的“超支化”聚合物。已经发现,这种类型的聚合物结构在稳定化带电粒子在通常被用作电泳显示器中的悬浮流体的非离子流体介质中的悬浮方面是非常有利的。可以通过在RGP步骤中使用的单体混合物中包括含有用于稳定的自由基聚合(SFRP)的引发基团的单体来制备相似类型的超支化聚合物,该SFRP引发基团被选择为使得其在RGP步骤中使用的条件下基本上不引发聚合。在RGP步骤结束之后,然后使粒子经受SFRP以制备超支化聚合物。The method in this section can include more than one stage and/or more than one type of polymerization. For example, in addition to using a monomer mixture containing at least one monomer (e.g., chloromethylstyrene) that provides a group for ATRP initiation sites, the particles are first subjected to the above-mentioned free radical polymerization method. Therefore, polymer chains containing ATRP initiation sites are formed on the particles. After the free radical polymerization is completed, the particles are then subjected to ATRP so that polymer side chains are formed by the ATRP initiation sites, thereby producing a "hyperbranched" polymer with a main chain formed by the RGP process and a side chain formed by ATRP. It has been found that this type of polymer structure is very advantageous in stabilizing the suspension of charged particles in a non-ionic fluid medium that is commonly used as a suspending fluid in an electrophoretic display. Similar types of hyperbranched polymers can be prepared by including a monomer containing an initiation group for stable free radical polymerization (SFRP) in the monomer mixture used in the RGP step, the SFRP initiation group being selected so that it does not substantially initiate polymerization under the conditions used in the RGP step. After the RGP step is completed, the particles are then subjected to SFRP to prepare hyperbranched polymers.
此外,可以使用具有一种能够共价地或离子键地键合至表面的基团和提供所需的可聚合或引发官能团的第二基团的任何双官能试剂将可聚合基团和引发剂附接到粒子的表面。两种基团的独立功能具有以下优点:在使方法适应于不同类型的粒子方面提供大的灵活性,同时保持相同的可聚合或引发功能,从而使工艺的后期阶段将只需要很少的因改变正被涂布的粒子的类型导致的改变(如果需要的话)。Furthermore, any bifunctional reagent having one group capable of covalently or ionically bonding to the surface and a second group providing the required polymerizable or initiating functionality can be used to attach the polymerizable group and initiator to the surface of the particle. The independent functionality of the two groups has the advantage of providing great flexibility in adapting the method to different types of particles while maintaining the same polymerizable or initiating functionality, so that later stages of the process will require only minimal changes (if necessary) due to changing the type of particle being coated.
在将用于提供期望的可聚合或引发官能团的试剂描述为“双官能”时,所述试剂可以包括每个类型的多于一个基团,并且实际上在一些情况下可能期望提供一种或两种类型的多于一个基团。例如,具有多于一个离子位点的聚合引发剂是已知的(诸如4,4'-偶氮二(4-氰基戊酸)),并且这种引发剂可用于该方法中。而且,双功能试剂可以具有聚合物的形式,其含有能够键合到粒子表面的重复单元和具有期望的可聚合或引发官能团的其它重复单元,并且这种聚合的双官能试剂通常将包括这两种类型的多个重复单元。Where a reagent for providing the desired polymerizable or initiating functional group is described as "bifunctional", the reagent may include more than one group of each type, and indeed in some cases it may be desirable to provide more than one group of one or both types. For example, polymerization initiators having more than one ionic site are known (such as 4,4'-azobis(4-cyanovaleric acid)), and such initiators may be used in the method. Furthermore, the bifunctional reagent may be in the form of a polymer containing repeating units capable of bonding to the particle surface and other repeating units having the desired polymerizable or initiating functional group, and such polymeric bifunctional reagents will typically include multiple repeating units of both types.
使用的可聚合和引发基团可以是本领域已知的任何一种,条件是相关基团与用于将它们附接到粒子表面的反应是相容的。许多示例在美国专利No.6,822,782中给出。The polymerizable and initiating groups used may be any of those known in the art, provided that the groups in question are compatible with the reaction used to attach them to the particle surface. Many examples are given in US Patent No. 6,822,782.
通常,由上述表面接枝方法制备的粒子具有按重量约1至约15%的化学键合至粒子表面或在粒子表面周围交联的聚合物。颜料表面附接有毛状聚合物链。聚合物链部分地或完全地溶解在电泳流体中。Typically, particles prepared by the surface grafting method described above have from about 1 to about 15% by weight of polymer chemically bonded to or cross-linked around the particle surface. The pigment surface has hairy polymer chains attached. The polymer chains are partially or completely dissolved in the electrophoretic fluid.
II.可替换的表面改性方法:II. Alternative surface modification methods:
另一种类型的表面改性方法产生具有封装在聚合物壳体或基质内的一个或多个核心粒子的粒子。聚合物壳体或基质在电泳流体中是不可溶的。封装的粒子上有聚合物链作为稳定剂,以有助于粒子可分散在电泳流体中。聚合物链可溶于流体中。Another type of surface modification method produces particles with one or more core particles encapsulated within a polymer shell or matrix. The polymer shell or matrix is insoluble in the electrophoretic fluid. The encapsulated particles have polymer chains attached as stabilizers to help disperse the particles in the electrophoretic fluid. The polymer chains are soluble in the fluid.
聚合物基质和稳定剂没有与原始颜料表面的化学键合。可以用合适的溶剂将它们洗掉。聚合物含量的范围可为按重量10-80%。The polymer matrix and stabilizer are not chemically bonded to the original pigment surface. They can be washed off with a suitable solvent. The polymer content can range from 10-80% by weight.
通常有机颜料可通过封装方法进行改性,因为它们通常具有以下表面的晶体结构:该表面非常难以化学键合额外分子。对有机颜料而言,表面接枝是重大挑战,因为其可能破坏发色团并改变颜料的颜色。Organic pigments are often modified by encapsulation methods because they typically have a crystalline structure with a surface that is very difficult to chemically bond additional molecules to. Surface grafting is a major challenge for organic pigments because it can destroy the chromophore and change the pigment's color.
这些方法描述于美国公开第2012-0199798号和第2013-0175479号中,其内容作为整体通过引用并入本文。These methods are described in U.S. Publication Nos. 2012-0199798 and 2013-0175479, the contents of which are incorporated herein by reference in their entireties.
核心粒子可以是上述那些有机或无机颜料中的任何一种。The core particle may be any of those organic or inorganic pigments described above.
核心粒子可以可选地进行表面处理。在形成最终粒子时,表面处理将改善核心颜料粒子与反应介质中单体的相容性或与单体的化学键合。作为示例,表面处理可以用具有诸如丙烯酸酯、乙烯基、-NH2、-NCO、-OH等的官能团的有机硅烷进行。这些官能团可以与单体发生化学反应。可以使用其它有机材料预处理颜料,包括作为分散剂的聚合物或低聚物,诸如聚丙烯酸酯、聚氨酯、聚脲、聚乙烯、聚酯、聚硅氧烷等。The core particles may optionally be surface treated. When the final particles are formed, the surface treatment improves the compatibility of the core pigment particles with the monomers in the reaction medium or improves chemical bonding with the monomers. For example, the surface treatment can be performed using organosilanes having functional groups such as acrylates, vinyl, -NH2 , -NCO, -OH, etc. These functional groups can chemically react with the monomers. Other organic materials can be used to pretreat the pigment, including polymers or oligomers that act as dispersants, such as polyacrylates, polyurethanes, polyureas, polyethylene, polyesters, polysiloxanes, etc.
表面处理也可以来自包括二氧化硅、氧化铝、氧化锌等或其组合的无机材料。硅酸钠或四乙氧基硅烷可用作二氧化硅涂层的常用前体。The surface treatment may also be from inorganic materials including silica, alumina, zinc oxide, etc. or combinations thereof. Sodium silicate or tetraethoxysilane may be used as common precursors for silica coatings.
此外,表面处理可以可选地具有将能够实现电荷产生或与电荷控制剂相互作用的官能团。Additionally, the surface treatment may optionally have functional groups that would enable charge generation or interaction with charge control agents.
核心粒子(多个核心粒子)和表面处理材料应该表现为一个单一的单元。然后核心粒子将通过以下工艺利用聚合物封装。The core particle(s) and the surface treatment material should behave as a single unit. The core particles are then encapsulated with a polymer through the following process.
II(a)分散聚合方法II(a) Dispersion Polymerization Method
无论是哪种情况,无机或有机核心粒子,最终的粒子都可以通过这种方法形成。在分散聚合期间,单体在核心颜料粒子周围聚合。被选择作为反应介质的溶剂必须是针对单体和形成的聚合物链两者的良好溶剂,但是对形成的聚合物壳体为非溶剂。例如,在Isopar的脂族烃溶剂中,单体甲基丙烯酸甲酯是可溶的;但在聚合之后,得到的聚甲基丙烯酸甲酯是不溶的。In either case, the final particles can be formed by this method, whether inorganic or organic core particles. During dispersion polymerization, monomers polymerize around the core pigment particles. The solvent chosen as the reaction medium must be a good solvent for both the monomers and the forming polymer chains, but a non-solvent for the forming polymer shell. For example, in the aliphatic hydrocarbon solvent of Isopar, the monomer methyl methacrylate is soluble; however, after polymerization, the resulting polymethyl methacrylate is insoluble.
聚合物壳体必须与其中分散有最终的粒子的溶剂完全不相容或相对不相容。合适的单体可以是上述那些,诸如苯乙烯、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸叔丁酯、甲基丙烯酸叔丁酯、乙烯基吡啶、N-乙烯基吡咯烷酮、丙烯酸2-羟乙酯、甲基丙烯酸2-羟乙酯、甲基丙烯酸二甲氨基乙酯等。The polymer shell must be completely incompatible or relatively incompatible with the solvent in which the final particles are dispersed. Suitable monomers can be those mentioned above, such as styrene, methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, vinyl pyridine, N-vinyl pyrrolidone, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, and the like.
为了合并用于电荷产生的官能团,可以在反应介质中加入共聚单体。共聚单体可以直接使复合颜料粒子带电或者与显示流体中的电荷控制剂相互作用,以给复合颜料粒子带来期望的电荷极性和电荷密度。合适的共聚单体可包括乙烯基苄基氨乙基氨丙基三甲氧基硅烷、甲基丙烯酰氧基丙基三甲氧基硅烷、丙烯酸、甲基丙烯酸、乙烯基磷酸、2-丙烯酰胺基-2-甲基丙磺酸、甲基丙烯酸2-(二甲基氨基)乙酯、N-[3-(二甲基氨基)丙基]甲基丙烯酰胺等。In order to incorporate functional groups for charge generation, comonomers can be added to the reaction medium. The comonomers can directly charge the composite pigment particles or interact with the charge control agent in the display fluid to impart the desired charge polarity and charge density to the composite pigment particles. Suitable comonomers can include vinylbenzylaminoethylaminopropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, acrylic acid, methacrylic acid, vinylphosphoric acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-(dimethylamino)ethyl methacrylate, N-[3-(dimethylamino)propyl]methacrylamide, and the like.
粒子的表面上的聚合物链通常由高分子量聚合物,诸如聚乙烯、聚丙烯、聚酯、聚硅氧烷或其混合物形成。聚合物链促进和稳定粒子在溶剂中的分散。The polymer chains on the surface of the particles are typically formed from high molecular weight polymers such as polyethylene, polypropylene, polyester, polysiloxane or mixtures thereof. The polymer chains facilitate and stabilize the dispersion of the particles in the solvent.
聚合物链可以是反应性的和可聚合的大分子单体,其吸附、结合或化学键合到正在形成的聚合物壳体的表面上。大分子单体作为聚合物链,确定了体系的粒径和胶体稳定性。The polymer chains can be reactive and polymerizable macromonomers that adsorb, bind, or chemically bond to the surface of the forming polymer shell. The macromonomers act as polymer chains, determining the particle size and colloidal stability of the system.
大分子单体可以是丙烯酸酯封端的或乙烯基封端的大分子,它们是合适的,因为丙烯酸酯或乙烯基团可以与反应介质中的单体共聚。The macromonomers may be acrylate terminated or vinyl terminated macromonomers, which are suitable because the acrylate or vinyl groups can copolymerize with the monomers in the reaction medium.
大分子单体优选具有长的末端R,其可以使最终的粒子稳定在烃溶剂中。The macromonomer preferably has a long terminal R, which can stabilize the final particles in hydrocarbon solvents.
一种类型的大分子单体是丙烯酸酯封端的聚硅氧烷(Gelest,MCR-M11,MCR-M17,MCR-M22),如下所示:One type of macromonomer is an acrylate-terminated polysiloxane (Gelest, MCR-M11, MCR-M17, MCR-M22), as shown below:
适用于该工艺的另一种类型的大分子单体是PE-PEO大分子单体,如下所示:Another type of macromonomer suitable for this process is the PE-PEO macromonomer, as shown below:
RmO-[-CH2CH2O-]n-CH2-苯基-CH=CH2 R m O-[-CH 2 CH 2 O-] n -CH 2 -phenyl-CH=CH 2
或RmO-[-CH2CH2O-]n-C(=O)-C(CH3)=CH2 Or R m O-[-CH 2 CH 2 O-] n -C(=O)-C(CH 3 )=CH 2
取代基R可以是聚乙烯链,n是1-60,且m是1-500。这些化合物的合成可见于DongriChao等人的Polymer Journal,Vol.23,no.9,1045(1991)和Koichi Ito等人的Macromolecules,1991,24,2348中。The substituent R may be a polyethylene chain, n is 1 to 60, and m is 1 to 500. The synthesis of these compounds can be found in Dongri Chao et al., Polymer Journal, Vol. 23, no. 9, 1045 (1991) and Koichi Ito et al., Macromolecules, 1991, 24, 2348.
另一种类型的适合的大分子单体是PE大分子单体,如下所示:Another type of suitable macromonomer is the PE macromonomer, as shown below:
CH3-[-CH2-]n-CH2O-C(=O)-C(CH3)=CH2 CH 3 -[-CH 2 -]n-CH 2 OC(=O)-C(CH 3 )=CH 2
在这种情况下,n为30-100。这种类型的大分子单体的合成可见于SeigouKawaguchi等人的Designed Monomers and Polymers,2000,3,263中。In this case, n is between 30 and 100. The synthesis of macromonomers of this type can be found in Seigou Kawaguchi et al., Designed Monomers and Polymers, 2000, 3, 263.
II(b)活性自由基分散聚合方法II(b) Living Radical Dispersion Polymerization Method
可替换地,可以通过活性自由基分散聚合制备粒子。该方法可应用于有机和无机颜料两者;但可能更适合用于有机颜料。Alternatively, the particles can be prepared by living free radical dispersion polymerization. This method is applicable to both organic and inorganic pigments; but may be more suitable for organic pigments.
活性自由基分散聚合技术与上述通过以分散于反应介质中的颜料粒子和单体开始工艺的分散聚合类似。Living free radical dispersion polymerization techniques are similar to the dispersion polymerization described above by starting the process with pigment particles and monomers dispersed in a reaction medium.
用以形成壳体的工艺中使用的单体可包括苯乙烯、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸叔丁酯、甲基丙烯酸叔丁酯、乙烯基吡啶、N-乙烯基吡咯烷酮、丙烯酸2-羟基乙酯、甲基丙烯酸2-羟基乙酯、甲基丙烯酸二甲氨基乙酯等。The monomers used in the process of forming the shell may include styrene, methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, vinyl pyridine, N-vinyl pyrrolidone, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, etc.
然而,在该可替换的工艺中,多个活性端形成在壳体的表面上。活性端可以通过将诸如TEMPO(2,2,6,6-四甲基-1-哌啶基氧基)、RAFT(可逆加成-裂解链转移)试剂等的试剂加入反应介质中产生,用于进行活性自由基聚合。However, in this alternative process, multiple active ends are formed on the surface of the shell. Active ends can be generated by adding reagents such as TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) or RAFT (reversible addition-fragmentation chain transfer) reagents to the reaction medium for living free radical polymerization.
在另外的步骤中,将第二单体添加到反应介质中以使活性端与第二单体反应以形成聚合物链。第二单体可以是丙烯酸月桂酯、甲基丙烯酸月桂酯、丙烯酸2-乙基己酯、甲基丙烯酸2-乙基己酯、丙烯酸己酯、甲基丙烯酸己酯、丙烯酸正辛酯、甲基丙烯酸正辛酯、丙烯酸正十八烷酯、甲基丙烯酸正十八烷酯等。In a further step, a second monomer is added to the reaction medium to react the active end with the second monomer to form a polymer chain. The second monomer can be lauryl acrylate, lauryl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, hexyl acrylate, hexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, n-octadecyl acrylate, n-octadecyl methacrylate, or the like.
聚合物链应与其中分散有粒子的溶剂相容以促进粒子在溶剂中的分散。The polymer chains should be compatible with the solvent in which the particles are dispersed to facilitate dispersion of the particles in the solvent.
用于聚合物链的单体可以是甲基丙烯酸羟乙酯和与非极性溶剂相容的其它丙烯酸酯的混合物,与非极性溶剂相容的其它丙烯酸酯诸如丙烯酸月桂酯、甲基丙烯酸月桂酯、丙烯酸2-乙基己酯、甲基丙烯酸2-乙基己酯、丙烯酸己酯、甲基丙烯酸己酯、丙烯酸正辛酯、甲基丙烯酸正辛酯、丙烯酸正十八烷酯、甲基丙烯酸正十八烷酯等。The monomers used for the polymer chain can be a mixture of hydroxyethyl methacrylate and other acrylates compatible with non-polar solvents, such as lauryl acrylate, lauryl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, hexyl acrylate, hexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, n-octadecyl acrylate, n-octadecyl methacrylate, etc.
本发明的优点包括色彩饱和度和色彩亮度,其可以通过L*a*b*颜色系统来测量。令人惊讶地发现,包括携带一定水平的电荷电位的有机彩色(非白色和非黑色)粒子和携带相同电荷极性的无机彩色(也是非白色和非黑色)粒子的电泳流体可显示比两种类型的相同地带电的有机彩色粒子共存于电泳流体中的电泳流体好得多的颜色性能。而且,本发明的系统允许以更短的波形转换两种颜色状态,导致更高的转换速度。Advantages of the present invention include color saturation and color brightness, which can be measured using the L*a*b* color system. Surprisingly, it has been discovered that an electrophoretic fluid comprising organic colored (non-white and non-black) particles carrying a certain level of charge potential and inorganic colored (also non-white and non-black) particles carrying the same charge polarity can exhibit significantly better color performance than an electrophoretic fluid in which both types of similarly charged organic colored particles coexist in the electrophoretic fluid. Furthermore, the system of the present invention allows for switching between two color states with shorter waveforms, resulting in higher switching speeds.
由于本发明的系统中的无机和有机颜料具有不同的表面改性化学,所以有机彩色颜料与无机彩色颜料的分离容易得多。这使得实现更饱和的色彩状态和更高的对比度。Because the inorganic and organic pigments in the system of the present invention have different surface modification chemistries, the separation of the organic color pigments from the inorganic color pigments is much easier. This allows for more saturated color states and higher contrast.
示例:Example:
在由本发明人进行的实验中,电泳流体具有多种类型的不同颜色的带电粒子。在多种类型的带电粒子中,红色和蓝色粒子带正电荷。In the experiments conducted by the present inventors, the electrophoretic fluid had multiple types of charged particles of different colors. Among the multiple types of charged particles, red and blue particles were positively charged.
在样品A中,红色和蓝色粒子两者都由有机颜料(即,分别为PR254和PB15)形成,并用相同的方法,即分散聚合进行表面处理。In Sample A, both the red and blue particles were formed from organic pigments (ie, PR254 and PB15, respectively) and were surface treated using the same method, namely, dispersion polymerization.
在样品B中,红色粒子由有机颜料(即,PR254)形成并且通过分散聚合进行表面处理,而蓝色粒子由无机颜料(即,PB28)形成并通过自由基聚合方法进行表面处理。In sample B, the red particles were formed of an organic pigment (ie, PR254) and surface-treated by dispersion polymerization, while the blue particles were formed of an inorganic pigment (ie, PB28) and surface-treated by a free radical polymerization method.
当这两个样品被驱动至不同的颜色状态时,发现样品A不能显示红色状态,因为有机红色粒子和有机蓝色粒子争夺流体中相同的电荷控制剂Solsperse 17K,并且两种类型的粒子不能充分分离。相比之下,样品B没有这样的问题,并且能够显示具有良好的色彩饱和度和亮度的红色和蓝色。When the two samples were driven to different color states, it was found that sample A was unable to display the red state because the organic red and organic blue particles competed for the same charge control agent, Solsperse 17K, in the fluid, and the two types of particles were not sufficiently separated. In contrast, sample B did not have this problem and was able to display red and blue with good color saturation and brightness.
本发明的电泳流体被填充在显示单元中。显示单元可以是美国专利No.6,930,818中所述的杯状微单元,其内容通过引用整体并入本文。显示单元也可以是其他类型的微容器,诸如微囊体、微通道或等同物,而不管其形状或尺寸如何。所有这些都在本申请的范围内。The electrophoretic fluid of the present invention is filled in a display unit. The display unit can be a cup-shaped microunit as described in U.S. Patent No. 6,930,818, the contents of which are incorporated herein by reference in their entirety. The display unit can also be other types of microcontainers, such as microcapsules, microchannels, or equivalents, regardless of their shape or size. All of these are within the scope of the present application.
尽管已经参考本发明的具体实施方案对本发明进行了描述,但是本领域技术人员应当理解,在不脱离本发明的范围的情况下,可以进行各种改变并且可以替换等同物。此外,可以进行许多修改以使特定情况、材料、组合物、工艺、工艺步骤或步骤适应于本发明的目的、精神和范围。所有这些修改都旨在在所附权利要求的范围内。Although the present invention has been described with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the scope of the present invention. In addition, many modifications may be made to adapt a particular situation, material, composition, process, process step or steps to the purpose, spirit and scope of the present invention. All such modifications are intended to be within the scope of the appended claims.
Claims (14)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201562159831P | 2015-05-11 | 2015-05-11 | |
US62/159831 | 2015-05-11 | ||
PCT/US2016/030931 WO2016182839A1 (en) | 2015-05-11 | 2016-05-05 | Electrophoretic display fluid |
Publications (2)
Publication Number | Publication Date |
---|---|
HK1244545A1 HK1244545A1 (en) | 2018-08-10 |
HK1244545B true HK1244545B (en) | 2021-04-30 |
Family
ID=
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107533269B (en) | Electrophoretic display fluid | |
US9423666B2 (en) | Additive for improving optical performance of an electrophoretic display | |
US20150185509A1 (en) | Method for improving image stability of electrophoretic fluid | |
US20170137632A1 (en) | Methods for modifying zeta potential of electrophoretic particles | |
US8902491B2 (en) | Additive for improving optical performance of an electrophoretic display | |
US9372380B2 (en) | Electrophoretic fluid | |
US9670367B2 (en) | Electrophoretic dispersion | |
US20140011913A1 (en) | Electrophoretic fluid | |
EP2997568A2 (en) | Color display device | |
HK40039087A (en) | Electrophoretic fluid | |
HK1244545B (en) | Electrophoretic display fluid | |
US10126627B2 (en) | Composite color particles | |
HK40006261A (en) | Color organic pigments and electrophoretic display media containing the same | |
KR20200103126A (en) | Composite particle and its manufacturing method |