KR100753487B1 - Colored electornic ink nanoparticles for electronic displays and preparation thereof - Google Patents

Colored electornic ink nanoparticles for electronic displays and preparation thereof Download PDF

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KR100753487B1
KR100753487B1 KR1020060044394A KR20060044394A KR100753487B1 KR 100753487 B1 KR100753487 B1 KR 100753487B1 KR 1020060044394 A KR1020060044394 A KR 1020060044394A KR 20060044394 A KR20060044394 A KR 20060044394A KR 100753487 B1 KR100753487 B1 KR 100753487B1
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nanoparticles
styrene
hydroxymethacrylate
divinylbenzene
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권용구
김태희
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인하대학교 산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
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    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0004—Coated particulate pigments or dyes
    • C09B67/0005—Coated particulate pigments or dyes the pigments being nanoparticles
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    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications

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Abstract

Provided are a multi-colored nanoparticle for electronic paper (e-paper) which is excellent in the clearness of color and is high in the mobility of electrophoresis, and a method for preparing the multi-colored nanoparticle. A multi-colored nanoparticle is the poly(styrene/divinyl benzene/2-hydroxy methacrylate) nanoparticle represented by a formula 1 where a hydroxyl group is introduced at the surface, and contains 2.5 wt% of 2-hydroxy methacrylate, wherein a reactive dye is dyed to the nanoparticle by covalent bond. Preferably the reactive dye is the Cibacron Blue 3G-A or Reactive Red 2 represented by a formula 2.

Description

전자종이 컬러 구현 다색 나노입자 및 그 제조방법 {Colored electornic ink nanoparticles for electronic displays and preparation thereof}Colored electrophoretic multicolor nanoparticles and a method of manufacturing the same {Colored electornic ink nanoparticles for electronic displays and preparation

도 1a 및 도 1b는 본 발명에 따라 제조된 폴리(스티렌-co-디비닐벤젠-co-2-하이드록시에틸렌메타크릴레이트)(이하, 'p(St-DVB-HEMA)'라 한다)의 염색 전후의 주사전자현미경 사진을 나타낸 것이다. 1A and 1B show poly (styrene-co-divinylbenzene-co-2-hydroxyethylenemethacrylate) (hereinafter referred to as 'p (St-DVB-HEMA)') prepared according to the present invention. Scanning electron micrographs before and after staining are shown.

도 2는 본 발명에 따라 제조된 p(St-DVB-HEMA) 나노입자를 파랑, 빨강으로 염색한 것을 나타낸 사진이다.Figure 2 is a photograph showing the blue, red stained p (St-DVB-HEMA) nanoparticles prepared according to the present invention.

본 발명은 전자종이(e-paper)에 컬러를 구현할 수 있는 다색 나노입자 및 그 제조방법, 특히 염색 방법에 관한 것이다.The present invention relates to multicolor nanoparticles capable of realizing color on an e-paper, and a method of manufacturing the same, in particular a dyeing method.

일반적으로 전자종이 디스플레이 또는 전기영동 디스플레이(Electrophoretic display)로 불리는 새로운 디스플레이는 종이와 현대적인 디스플레이의 장점을 겸비한 표시장치로 알려져 있다. New displays, commonly referred to as electronic paper displays or electrophoretic displays, are known as displays that combine the advantages of paper and modern displays.

전기영동현상은 어떤 입자가 매체(분산매체)에 현탁된 경우에 입자가 전기적으로 하전되고, 또한 전계가 하전입자에 인가되는 경우에 그들이 대향 전하를 가진 전극에 분산매체를 통해서 이동하는 현상이다. 이러한 현상을 이용하는 전자 잉크 또는 전기영동 디스플레이에 사용하기 위한 전기영동입자로 백색안료로는 산화티타늄(타이타니아), 흑색안료로는 잉크에 널리 사용되는 카본블랙 등이 일반적으로 사용되고 있다. 컬러 구현을 위한 다색안료의 경우 이온성 염료와 무기화합물과의 염으로 구성된 안료 등 많은 연구 개발이 진행 중이나 아직까지 적합한 안료가 제시되지 못하고 있는 실정이다. 또, 전기영동입자의 모양과 집합체의 수가 불균일하기 때문에 분산량의 조절이 어렵고 그리고 균일하게 분산시키는 것이 어렵다. Electrophoresis is a phenomenon in which when a particle is suspended in a medium (dispersion medium), the particles are electrically charged, and when an electric field is applied to the charged particles, they move through the dispersion medium to electrodes having opposite charges. Electrophoretic particles for use in electronic inks or electrophoretic displays using such a phenomenon are commonly used titanium oxide (Titania) as a white pigment, carbon black widely used in ink as a black pigment. In the case of multicolored pigments for color realization, many researches and developments such as pigments consisting of salts of ionic dyes and inorganic compounds are underway, but there are no suitable pigments yet. In addition, since the shape of the electrophoretic particles and the number of aggregates are nonuniform, it is difficult to control the dispersion amount and to disperse uniformly.

본 발명은 전기영동 디스플레이의 컬러 구현을 위하여 다색 나노입자, 특히 다색 가교된 폴리(스티렌/디비닐벤젠/2-하이드록시메타크릴레이트) 나노입자를 제공하는 것을 그 목적으로 한다. The present invention aims to provide multicolor nanoparticles, in particular multicolor crosslinked poly (styrene / divinylbenzene / 2-hydroxymethacrylate) nanoparticles, for color realization of an electrophoretic display.

또한, 입자의 모양과 집합체의 수가 균일하여 분산량의 조절 및 분산이 용이한 다색 p(St-DVB-HEMA) 나노입자를 제공하는 것을 목적으로 한다. It is also an object of the present invention to provide multicolored p (St-DVB-HEMA) nanoparticles in which the shape and number of aggregates of the particles are uniform so that the amount of dispersion and the dispersion are easily controlled.

또, 본 발명은 섬유의 염색 시 가장 흔히 쓰이는 셀룰로오스계 섬유의 하이드록시기와 반응염료가 화학적 공유결합으로 염착되는 성질을 이용하여 p(St-DVB-HEMA) 입자를 염색하는 방법을 제공하려고 한다. In addition, the present invention is to provide a method for dyeing p (St-DVB-HEMA) particles using the property that the hydroxy group and the reactive dye of the cellulose fibers which are most commonly used when dyeing the fibers are dyes by chemical covalent bonds.

본 발명의 적절한 실시 형태에 따르면, 하이드록시기가 표면에 도입된 폴리(스티렌/디비닐벤젠/2-하이드록시메타크릴레이트) 나노입자에 반응염료가 염색된 하기 화학식 1로 나타내어지는 다색 폴리(스티렌/디비닐벤젠/2-하이드록시메타크릴레이트) 나노입자가 제공된다.According to a preferred embodiment of the present invention, the polychromic (styrene) represented by the following formula (1) in which the dye is reacted to the poly (styrene / divinylbenzene / 2-hydroxymethacrylate) nanoparticles having a hydroxyl group introduced thereon / Divinylbenzene / 2-hydroxymethacrylate) nanoparticles are provided.

[화학식 1][Formula 1]

Figure 112006034499043-pat00001
Figure 112006034499043-pat00001

본 발명의 다른 적절한 실시 형태에 따르면, 반응염료는 아래 화학식 2로 나타내어지는 시바크론 블루(Cibacron Blue) 3G-A와 C. I. 반응성 빨강염료 2를 사용할 수 있다. According to another suitable embodiment of the present invention, the reaction dye may use Cibacron Blue 3G-A and C. I. reactive red dye 2 represented by the following formula (2).

[화학식 2][Formula 2]

Figure 112006034499043-pat00002
Figure 112006034499043-pat00002

본 발명의 또 다른 적절한 실시 형태에 따르면, 스티렌, 디비닐벤젠 및 2-하이드록시메타크릴레이트를 개시제로 과황산암모늄을 사용하여 무유화 중합법으로 중합하여 하이드록시기가 도입된 폴리(스티렌/디비닐벤젠/2-하이드록시메타크릴레이트) 나노입자를 제조하는 단계; 및 상기 폴리(스티렌/디비닐벤젠/2-하이드록시메타크릴레이트) 나노입자를 분산염료로 염색하는 단계를 포함하는 다색 폴리(스티렌/디비닐벤젠/2-하이드록시메타크릴레이트) 나노입자의 제조방법이 제공된다. According to another suitable embodiment of the present invention, a poly (styrene / di) having a hydroxyl group introduced by polymerization of styrene, divinylbenzene and 2-hydroxymethacrylate by an emulsion-free polymerization method using ammonium persulfate as an initiator. Preparing vinylbenzene / 2-hydroxymethacrylate) nanoparticles; And dyeing the poly (styrene / divinylbenzene / 2-hydroxy methacrylate) nanoparticles with a disperse dye of the multicolored poly (styrene / divinylbenzene / 2-hydroxymethacrylate) nanoparticles. A manufacturing method is provided.

본 발명의 또 다른 적절한 실시 형태에 따르면, 반응염료를 사용한 염색은 50℃의 온도에서 24시간 동안 이루어지는 것이 바람직하다. According to another suitable embodiment of the present invention, the dyeing using the reaction dye is preferably performed for 24 hours at a temperature of 50 ℃.

이하 본 발명을 더 상세히 설명한다.Hereinafter, the present invention will be described in more detail.

본 발명은 전자종이 컬러 구현을 위하여 무유화 에멀젼 중합법을 이용하여 p(St-DVB-HEMA)나노입자의 표면에 음전하를 띠게 하고, 반응염료로 염색하여 선명 한 전자종이 컬러를 구현할 수 있는 하기 화학식 1로 나타내어지는 다색 p(St-DVB-HEMA) 나노입자를 제공할 수 있다. The present invention has a negative charge on the surface of p (St-DVB-HEMA) nanoparticles by using an emulsion-free emulsion polymerization method for the electronic paper color implementation, can be colored with a reaction dye to achieve a vivid electronic paper color It is possible to provide a multi-color p (St-DVB-HEMA) nanoparticles represented by the formula (1).

[화학식 1][Formula 1]

Figure 112006034499043-pat00003
Figure 112006034499043-pat00003

무유화 에멀젼 중합법은 나노 규모의 직경을 가진 단분산 중합체 입자를 제조하기 위한 유용한 방법의 하나로 알려져 있다. 이 방법을 이용하면 사용하는 개시제의 전하를 띠는 그룹이 제조된 나노입자의 표면에 존재하여 입자를 안정화시킴과 동시에 전하를 부여하게 되는 효과를 얻을 수 있다. Emulsified emulsion polymerization is known as one of the useful methods for producing monodisperse polymer particles having nanoscale diameters. By using this method, the charged group of the initiator can be present on the surface of the prepared nanoparticles to stabilize the particles and at the same time give the charge.

반응염료는 화학구조상 트리아진기에 클로라이드를 포함하고 있기 때문에 알칼리 조건에서 친핵성 치환 반응에 의해 입자의 하이드록시기와 공유결합이 가능하다. 그러므로 물리적인 흡착으로 염색하는 것과 비교할 때 탈착의 위험이 없다. 또한 반응염료의 경우 -SO3Na기와 같은 여러 개의 음이온성 수용화기를 가지고 있으므로 음이온성 표면 전하를 띠는 입자에 고착할 경우 입자의 표면 전하를 증가시키는 효과도 기대할 수 있어서, 폴리머 입자를 합성할 때 반응염료와 반응 가능한 관능기의 도입이 필요하다. 본 발명의 경우는 2-하이드록시메타크릴레이트(2-hydroxymethacrylate)를 단량체로 첨가하여, 처음 중합할 때부터 입자의 표면에 하 이드록시기를 도입하여 제조공정을 축소하고 반응염료의 염색성 향상을 도모하였다.Since the reaction dye contains chloride in the triazine group due to its chemical structure, it is possible to covalently bond to the hydroxyl group of the particles by nucleophilic substitution reaction under alkaline conditions. Therefore, there is no risk of desorption compared with dyeing by physical adsorption. In addition, since the reactive dyes have a number of anionic acceptors such as -SO 3 Na group, it is possible to expect the effect of increasing the surface charge of the particles when they are adhered to the particles having anionic surface charge. It is necessary to introduce a functional group capable of reacting with a reactive dye. In the case of the present invention, 2-hydroxymethacrylate is added as a monomer, and since the first polymerization, a hydroxyl group is introduced on the surface of the particles to reduce the manufacturing process and improve dyeing properties of the reaction dye. It was.

본 발명의 p(St-DVB-HEMA) 나노입자를 제조하기 위하여, 단량체로는 스티렌, 디비닐벤젠 및 2-하이드록시메타크릴레이트를, 개시제는 음이온을 띠는 과황산암모늄(APS, ammonium persulfate)를 사용하였다. 이때 중합온도는 60 내지 80℃, 바람직하게는 70℃로 하고, 중합시간은 13 내지 15시간, 바람직하게는 14시간으로 한다. In order to prepare p (St-DVB-HEMA) nanoparticles of the present invention, monomers include styrene, divinylbenzene and 2-hydroxymethacrylate, and an initiator is anionic ammonium persulfate (APS). ) Was used. At this time, the polymerization temperature is 60 to 80 ℃, preferably 70 ℃, the polymerization time is 13 to 15 hours, preferably 14 hours.

가교된 입자를 중합하기 위해 DVB은 전체 단량체 대비 18 내지 22중량%로 첨가하면 되고, 바람직하게는 20중량%의 중량비로 첨가한다.In order to polymerize the crosslinked particles, DVB may be added in an amount of 18 to 22% by weight based on the total monomers, and preferably in a weight ratio of 20% by weight.

본 발명의 가교된 p(St-DVB-HEMA)입자는 입자 제조 후 유독한 유기용매에서 실시되는 반응과정이 없이 중합하면서 표면에 하이드록시기의 도입이 가능하다. 이 경우에도 HEMA는 OH기로 인해 물과 친화성이 있으므로 중합하는 동안 물과 인접한 입자의 표면에 위치한다. The cross-linked p (St-DVB-HEMA) particles of the present invention are capable of introducing a hydroxyl group on the surface while polymerizing without producing a particle and then performing a reaction process in a toxic organic solvent. Even in this case, HEMA is affinity with water due to the OH group, so it is located on the surface of particles adjacent to water during the polymerization.

HEMA 사용량은 나노입자 전체 중량 대비 2.5중량%로 사용하는 것이 바람직하다. 이는 HEMA를 도입하는 양이 많을수록 입자의 표면이 거칠어지고, 2.5 wt%를 넘어설 경우 안정한 입자의 형성이 불가능하기 때문이다. HEMA amount is preferably used at 2.5% by weight based on the total weight of the nanoparticles. This is because the larger the amount of HEMA introduced, the rougher the surface of the particles, and when it exceeds 2.5 wt%, it is impossible to form stable particles.

무유화 중합법으로 중합된 전하를 띠고 있는 입자를 반응염료로 염색을 하여, 반응염료가 가진 전하가 더 부가되어 전기영도 이동도가 향상된 다색 p(St-DVB-HEMA) 나노입자를 제조한다. Particles having a charge polymerized by the non-emulsification polymerization method are dyed with a reaction dye to prepare multicolored p (St-DVB-HEMA) nanoparticles having improved electrophoretic mobility by further adding a charge of the reaction dye.

본 발명에서 반응염료는 시바크론 블루(Cibacron Blue) 3G-A와 C. I. 반응성 빨강염료 2를 사용하였다. 이들 염료는 아래 화학구조식 2로 나타낸 바와 같이 공통적으로 트리아진기에 클로라이드와 같은 반응성기를 가지고 있다. p(St-DVB-HEMA) 나노입자의 표면에 생성된 하이드록시기와 클로라이드 반응기가 공유결합하여 염착이 이루어진다. In the present invention, as the reaction dye, Cibacron Blue 3G-A and C. I. Reactive Red Dye 2 were used. These dyes commonly have a reactive group, such as chloride, in the triazine group, as shown by chemical formula 2 below. The hydroxyl group formed on the surface of the p (St-DVB-HEMA) nanoparticles is covalently bonded to the chloride reactor to form a dye.

[화학식 2][Formula 2]

Figure 112006034499043-pat00004
Figure 112006034499043-pat00004

아래에서 실시 예를 들어 본 발명을 더욱 상세히 설명하나, 본 발명에 따른 실시 예들은 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시 예들에 한정되는 것으로 해석되어서는 안 된다. Hereinafter, the present invention will be described in more detail with reference to the following examples, but the embodiments according to the present invention can be modified in various forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. do.

실시 예Example

실시 예1Example 1

나노입자의 제조Preparation of Nanoparticles

스티렌, 디비닐벤젠 및 2-하이드록시메타크릴레이트를 개시제 과황산암모늄( APS, ammonium persulfate)를 사용하여 무유화 공중합법으로 가교된 공중합체 나노입자를 제조한다. 이때, 물 285 ml에 단량체의 조성은 스티렌 9g, 디비닐벤젠 3g, 2-하이드록시메타크릴레이트 3g이며 개시제 APS는 0.392g을 이용하였다. 염의 농도는 NaCl 0.05 g으로 맞추었다.교반기, 환류 콘덴서 및 질소 주입 시스템이 장착된 250ml 둥근 플라스크를 이용하였고 APS 개시제를 300 rpm 속도로 교반하면서 반응기에 첨가했다. 그리고나서 70℃온도에서 14시간 동안 중합했다. 중합 후, 입자를 증류수에서 원심분리/재분산을 세 번 이상 순환 실시하여 정제하였다. 마지막으로 동결건조하여 나노입자를 얻었다. Styrene, divinylbenzene and 2-hydroxymethacrylate are prepared using an initiator ammonium persulfate (APS, ammonium persulfate) to prepare copolymer nanoparticles crosslinked by an emulsion-free copolymerization method. At this time, the composition of the monomer in 285 ml of water was 9 g of styrene, 3 g of divinylbenzene, 3 g of 2-hydroxymethacrylate, and 0.392 g of initiator APS was used. The concentration of salt was adjusted to 0.05 g NaCl. A 250 ml round flask equipped with a stirrer, reflux condenser and nitrogen injection system was used and the APS initiator was added to the reactor with stirring at 300 rpm. Then, the polymerization was carried out at 70 ° C. for 14 hours. After the polymerization, the particles were purified by centrifugation / redispersion three times or more in distilled water. Finally lyophilized to obtain nanoparticles.

p(p ( StSt -- DVBDVB -- HEMAHEMA ) 입자의 염색) Dyeing of particles

표면에 하이드록시기가 도입된 p(St-DVB-HEMA) 나노입자 0.5 g을 4 g/L의 반응염료 수용액에 분산시켰다. 이후, 1M NaOH 수용액을 이용하여 pH 12로 조절하였고, 50 ℃에서 24시간 염색하였다. 염색 후, 수 회 원심분리하여 세척하고, 동결건조하여 입자를 얻었다.0.5 g of p (St-DVB-HEMA) nanoparticles having a hydroxyl group introduced on the surface thereof was dispersed in 4 g / L of an aqueous reaction dye solution. Thereafter, the mixture was adjusted to pH 12 using 1M aqueous NaOH solution, and stained at 50 ° C. for 24 hours. After dyeing, centrifugation was washed several times, and lyophilized to obtain particles.

제조된 입자의 평가Evaluation of the Particles Prepared

본 발명에 따라 제조된 나노입자의 모양 및 분산 상태를 전자주사현미경(SEM)으로 검사하였다. 열전이온도는 열 분석기 DSC 2920을 사용하여 10℃/min 속도로 가온하면서 질소분위기하에서 측정했다. US/VIS 스펙트로미터를 사용하여 흡광도를 측정하였다. FTIR 스펙트럼을 실시했다. 전기영동 이동도는 ELS-8000으로 동적 빛 산란(dynamic light scattering, DSC)로 결정했다.The shape and dispersion state of the nanoparticles prepared according to the present invention were examined by electron scanning microscope (SEM). The heat transition temperature was measured under a nitrogen atmosphere by heating at a rate of 10 ° C./min using a thermal analyzer DSC 2920. Absorbance was measured using a US / VIS spectrometer. FTIR spectra were carried out. Electrophoretic mobility was determined by dynamic light scattering (DSC) with the ELS-8000.

본 발명에 따라 제조된 p(St-DVB-HEMA) 나노입자의 크기 및 분산 상태는 주사전자현미경으로 검사하였고, 그 결과를 도 1a 및 도 1b에 나타내었다. The size and dispersion state of the p (St-DVB-HEMA) nanoparticles prepared according to the present invention were examined by scanning electron microscopy, and the results are shown in FIGS. 1A and 1B.

p(St-DVB-HEMA)에 염색된 입자의 색깔은 도 2에 나타낸 바와 같다. 반응염료로 염색된 칼라입자는 입자를 중합할 때부터 음이온성 개시제(APS)를 사용했기 때문에 무유화 중합 후 (-)전하를 나타낸다. 물에 분산된 입자가 나타내는 표면 전하 값을 제타 분석기(zeta analyzer)를 이용하여 측정하였으며 염색 후 제타 전위(zeta potential)는 41.7 mV, 이동도(mobility)는 3.021x10-4 cm2/Vs의 값을 보였다. The color of the particles stained with p (St-DVB-HEMA) is as shown in FIG. 2. Color particles stained with a reactive dye show a negative charge after the emulsion-free polymerization because the anionic initiator (APS) was used from the time of polymerization of the particles. The surface charges of the particles dispersed in water were measured using a zeta analyzer. After staining, the zeta potential was 41.7 mV and the mobility was 3.021x10 -4 cm 2 / Vs. Showed.

본 발명에 따라 제조된 나노입자는 색깔이 선명하고, 전기영동 이동도가 높아서, 전자종이에서 선명한 컬러를 구현할 수 있다. The nanoparticles prepared according to the present invention are vivid colors, high electrophoretic mobility, it is possible to implement a vivid color on the electronic paper.

Claims (3)

전자종이용 다색 나노입자에 있어서,In the multi-color nanoparticles for electronic paper, 상기 나노입자는 나노입자 전체 중량 대비 2.5중량%의 2-하이드록시메타크릴레이트를 포함하고 그리고 하기 화학식 1로 나타낸 하이드록시기가 표면에 도입된 폴리(스티렌/디비닐벤젠/2-하이드록시메타크릴레이트) 나노입자이고, The nanoparticles include 2.5% by weight of 2-hydroxymethacrylate relative to the total weight of the nanoparticles, and a poly (styrene / divinylbenzene / 2-hydroxymethacryl having a hydroxyl group represented by the following Formula 1 introduced on the surface thereof. Rate) nanoparticles, 상기 나노입자에 반응염료가 공유결합으로 염착된 것을 특징으로 하는 전자종이용 다색 나노입자. Electrochromic multi-color nanoparticles, characterized in that the reaction dye is covalently dyed to the nanoparticles. [화학식 1][Formula 1]
Figure 112007031500235-pat00005
Figure 112007031500235-pat00005
 제 1항에 있어서, 상기 반응염료는 아래 화학식 2로 나타내어지는 시바크론 블루(Cibacron Blue) 3G-A와 C. I. 반응성 빨강염료 2가 되는 것을 특징으로 하는 전자종이용 다색 나노입자.The multicolor nanoparticle for electronic paper according to claim 1, wherein the reaction dye is Cibacron Blue 3G-A and C. I. Reactive red dye 2. [화학식 2][Formula 2]
Figure 112007031500235-pat00006
Figure 112007031500235-pat00006
 전자종이용 다색 나노입자의 제조방법에 있어서,In the manufacturing method of multi-color nanoparticles for electronic paper, 스티렌, 디비닐벤젠 및 2-하이드록시메타크릴레이트를 개시제로 과황산암모늄을 사용하여 무유화 중합법으로 중합하여 하이드록시기가 도입된 폴리(스티렌/디비닐벤젠/2-하이드록시메타크릴레이트) 나노입자를 제조하는 단계; 및Poly (styrene / divinylbenzene / 2-hydroxymethacrylate) having a hydroxyl group introduced by polymerization of styrene, divinylbenzene and 2-hydroxymethacrylate as an initiator using an ammonium persulfate as an initiator. Preparing nanoparticles; And 상기 폴리(스티렌/디비닐벤젠/2-하이드록시메타크릴레이트) 나노입자를 분산염료로 염색하는 단계를 포함하는 것을 특징으로 하는 다색 폴리(스티렌/디비닐벤젠/2-하이드록시메타크릴레이트) 나노입자의 제조방법. Multicolored poly (styrene / divinylbenzene / 2-hydroxymethacrylate), characterized in that it comprises dyeing the poly (styrene / divinylbenzene / 2-hydroxymethacrylate) nanoparticles with a disperse dye. Method for producing nanoparticles.
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US5597485A (en) 1988-05-13 1997-01-28 Vilmax S.A. Process for separating proteins
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KR100589125B1 (en) 2004-07-28 2006-06-14 최순자 Process for preparing monodisperse polymer particles by soap-free emulsion polymerization

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US4017476A (en) 1974-03-15 1977-04-12 Mobil Oil Corporation Preparation of finely divided styrene-divinylbenzene organic pigments
US5597485A (en) 1988-05-13 1997-01-28 Vilmax S.A. Process for separating proteins
US20050271970A1 (en) 2004-06-04 2005-12-08 Samsung Electronics Co., Ltd. Preparation method of toner having micro radius
KR100589125B1 (en) 2004-07-28 2006-06-14 최순자 Process for preparing monodisperse polymer particles by soap-free emulsion polymerization

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US8289352B2 (en) 2010-07-15 2012-10-16 HJ Laboratories, LLC Providing erasable printing with nanoparticles

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