WO2012141528A2 - Method for surface-treating electronic paper particle using titanium dioxide additive and electronic paper particle using titanium dioxide additive manufactured thereby - Google Patents

Method for surface-treating electronic paper particle using titanium dioxide additive and electronic paper particle using titanium dioxide additive manufactured thereby Download PDF

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Publication number
WO2012141528A2
WO2012141528A2 PCT/KR2012/002818 KR2012002818W WO2012141528A2 WO 2012141528 A2 WO2012141528 A2 WO 2012141528A2 KR 2012002818 W KR2012002818 W KR 2012002818W WO 2012141528 A2 WO2012141528 A2 WO 2012141528A2
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titanium dioxide
particles
electronic paper
surface treatment
external additive
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PCT/KR2012/002818
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French (fr)
Korean (ko)
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WO2012141528A3 (en
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이상국
최경호
신교직
김은경
정승용
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한국생산기술연구원
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Publication of WO2012141528A3 publication Critical patent/WO2012141528A3/en

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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/165—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on translational movement of particles in a fluid under the influence of an applied field
    • G02F1/166—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on translational movement of particles in a fluid under the influence of an applied field characterised by the electro-optical or magneto-optical effect
    • G02F1/167—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on translational movement of particles in a fluid under the influence of an applied field characterised by the electro-optical or magneto-optical effect by electrophoresis
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/165—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on translational movement of particles in a fluid under the influence of an applied field
    • G02F1/1675—Constructional details
    • G02F2001/1678—Constructional details characterised by the composition or particle type

Definitions

  • the present invention relates to a surface treatment method for particles of electronic paper using titanium dioxide external additives and to particles for electronic paper using titanium dioxide external additives prepared using the same. More specifically, unlike the conventional method, a solution adsorption method is used. By chemically adsorbing the external additives to the particles, forming functional groups, and surface treating them, the titanium dioxide external additives which not only impart strong charges to the particles and prevent aggregation among the particles, but also significantly improve durability and flowability
  • the present invention relates to a surface treatment method of particles for electronic paper using, and to particles for electronic paper using titanium dioxide external additive prepared using the same.
  • the dual electronic paper technology uses the rapid movement of microparticles by an electric field to electrostatically move charged particles floating in a certain space to display colors. Therefore, even if the voltage is removed, the image does not disappear because there is no change in the position of the particles, so that the effect as if printed on paper is printed. In other words, it does not emit light by itself, but the visual fatigue is very low, so it is possible to enjoy a comfortable viewing like a real book, and the panel's flexibility is high enough to bend and the thickness can be formed very thin. There is great expectation as a display device technology. In addition, as mentioned, power consumption is extremely low since the displayed image is maintained for a long time unless the panel is reset, thereby making it excellent as a portable display device. In particular, low prices due to simple processes and low cost materials are expected to contribute to the popularization of electronic paper.
  • Electronic paper techniques generally used include electrophoretic methods for microencapsulating a dispersion consisting of dispersed particles and a colored solution, and disposing the dispersion liquid between opposing substrates to cause particles to move in the liquid; Without using a solution, two or more kinds of particles having different colors and charging characteristics are enclosed between at least one transparent substrate, and an electric field is applied to the particles from an electrode pair consisting of electrodes formed on one or both of the substrates.
  • a collision charging method has been proposed in which an charged particle having a different polarity is moved and moved in different directions by a Coulomb force to display an image.
  • a technique for forming a charged particle having a fluidity (hereinafter referred to as a 'fluid particle') should be accompanied, and the fluid particle may have a coupling agent or the like on the surface of the particle.
  • liquidity is shown by coating the same external additive.
  • the flowable particles include an external blending method using a mixer by adding an external additive to a dispersion solvent containing the particles.
  • the flowable particles in this manner, the particles and the external additives are physically bonded, due to the limitation of the durability of the physical bonds, there is a problem that the external components easily fall off.
  • a polymerization method according to emulsion polymerization, dispersion polymerization or suspension polymerization is used. Since the polymer particles thus prepared mostly exhibit lipophilic surface properties, hydrophilic functional groups are formed on the surface. It is difficult to apply a new polymerization method for the introduction of the hydrophilic functional group in order to obtain the polymer particles bound, and unlike most commercial lipophilic polymer particles, very high in order to obtain the polymer particles into which the hydrophilic functional groups are introduced. In addition to the cost, there is a problem in that a cumbersome and inexpensive manufacturing method such as using a surfactant is used.
  • the present invention is to solve the above problems, unlike the prior art, by using a solution adsorption method, not only can adsorb the external additives to the particles more quantitatively and uniformly, but also due to chemical bonding, significantly improve the durability
  • An object of the present invention is to provide a surface treatment method for an electronic paper particle using a titanium dioxide external additive, and an electronic paper particle using a titanium dioxide external additive prepared using the same.
  • the surface treatment of the particles for electronic paper using titanium dioxide external additive which enhances the durability and fluidity of the particles by reacting the titanium dioxide formed with hydrochloric acid, glutaraldehyde and amino groups in the optimum content ratio by the solution adsorption method It is an object of the present invention to provide an electronic paper particle using the method and the titanium dioxide external additive prepared using the same.
  • An object of the present invention is to provide an electronic paper particle additive for electronic paper using titanium dioxide and an electronic paper particle additive for titanium paper prepared using the same.
  • the surface treatment method of the particle for electronic paper using the titanium dioxide external additive according to the present invention comprises adding bare particles to a second solvent to which titanium dioxide having an amino group is added, followed by dispersion and reaction.
  • the reaction preparation step the titanium dioxide having the amino group
  • the purification step of purifying the titanium dioxide by heat treatment at 300 to 500 °C for 15 to 30 hours
  • an amino group substitution step of adding titanium dioxide to the first solvent and reacting to produce titanium dioxide having an amino group.
  • the second solvent is characterized in that the isopropyl alcohol (Isopropyl Alcohol), in the reaction preparation step, the bare particles are prepared by synthesizing a monomer, a polymerization initiator and an ionic monomer.
  • the ionic monomer is characterized in that any one of styrene sulfonic acid (Styrene sulfonic acid) or [2- (methacryloxy) ethyl] trimethyl ammonium chloride.
  • the monomer is at least one of methyl methacrylate, ethylene terephthalate, styrenesulfonate, vinyl acetate, methyl styrene, acrylic acid, butyl methacrylate, ethyl methacrylate, 2-ethylhexyl acrylate or N-vinyl caprolactam
  • the polymerization initiator is at least one of a peroxide compound or an azo compound.
  • the titanium dioxide having the amino group is added to 0.1 parts by weight based on 100 parts by weight of the second solvent, with respect to 100 parts by weight of the second solvent, the bare particles Is characterized by adding 1 to 5 parts by weight.
  • the hydrochloric acid and glutaraldehyde are added to 60 parts by weight to 90 parts by weight, respectively, with respect to 100 parts by weight of the second solvent.
  • the hydrochloric acid and glutaraldehyde are added while stirring using a magnetic bar at 10 to 30 ° C.
  • the reaction time is characterized in that 1 to 3 hours
  • the first solvent is characterized in that toluene.
  • the amino group substitution step the reaction solution manufacturing step of preparing a reaction solution by adding the titanium dioxide to the first solvent, and then dispersing; A heating step of heating the reaction solution under a nitrogen atmosphere; An ethoxysilane addition step of adding (3-aminopropyl) triethoxysilane to the reaction solution; And a stirring step of stirring the reaction solution.
  • the titanium dioxide is characterized in that 20 to 50 parts by weight with respect to 100 parts by weight of the first solvent, the heating step, the temperature of the reaction solution of 60 °C to 90 °C It is characterized by maintaining at a temperature.
  • the (3-aminepropyl) triethoxysilane is characterized in that 20 to 50 parts by weight, the stirring step, the reaction solution 60 It is characterized by stirring for 15 to 30 hours at a temperature of °C to 90 °C.
  • the surface treatment method of the particle for electronic paper using the titanium dioxide external additive of the present invention and the particle for electronic paper using the titanium dioxide external additive prepared by using the same unlike the conventional method, by using a solution adsorption method, Not only can the external additive be adsorbed to the particles uniformly, but also due to the chemical bonding, the durability can be significantly improved.
  • the external additive improves the contrast ratio in the electronic paper apparatus. There is an advantage to this.
  • 1 is a flow chart sequentially showing a manufacturing method of the particle external additive for electronic paper using titanium dioxide according to the present invention.
  • Figure 2 is a cross-sectional view showing the particles for electronic paper using the titanium dioxide external additive prepared by using the surface treatment method of the electronic paper particles using the titanium dioxide external additive according to the present invention.
  • the surface treatment method of the electronic paper particles using the titanium dioxide external additive according to the present invention the purification step (S10), amino-substituted step (S20), reaction preparation step (S30) and particle surface treatment It characterized in that it comprises a step (S40).
  • the reaction preparation step (S30) is a step of preparing a reaction preparation solution by adding the bare particles to the second solvent to which titanium dioxide having an amino group is added, and then dispersed. This is a step of preparing a reaction by dispersing bare particles and an external additive in a solvent before starting the particle surface treatment reaction.
  • the second solvent may be any solvent that facilitates the dispersion of the titanium dioxide external additive and the bare particles, and may help the particle surface treatment reaction thereafter, but several experiment results In the present invention, it is most effective to use isopropyl alcohol, which is preferably used.
  • the bare particles are preferably prepared by synthesizing a monomer, a polymerization initiator and an ionic monomer.
  • the monomers, the polymerization initiator, and the ionic monomer are added to the solvent, followed by stirring to synthesize the bare particles.
  • the solvent may be any material that does not interfere with particle synthesis and may help the reaction, but methanol is most preferably used.
  • the monomer is methyl methacrylate, ethylene terephthalate, styrene sulfonate, vinyl acetate, methyl styrene, acrylic acid, butyl methacrylate, ethyl methacrylate, 2-ethylhexyl acrylate or N-vinyl caprolactam It is preferable to use at least one, and the above materials may be copolymerized.
  • the polymerization initiator may use any free radical polymerization initiator capable of triggering an emulsion-free polymerization, but in the present invention, at least one of a peroxide compound or an azo compound is preferable, and the peroxide compound is, in principle, an inorganic peroxide, For example alkyl hydroperoxides, examples being tert-butyl, p-mentyl and cumyl hydroperoxide, and also dialkyl or diaryl peroxides such as di-tert-butyl peroxide or dicumyl peroxide Azo compounds are mainly 2,2'-azobis (isobutylonitrile), 2,2'-azobis (isobutyramidine) hydrochloride (2,2'-azobis (isobutyramidine) hydrochloride) It is most efficient to use 'AIBN') as a polymerization initiator.
  • a peroxide compound or an azo compound is preferable, and the peroxide compound is, in principle, an inorgan
  • the ionic monomer is preferably either styrene sulfonic acid or [2- (methacryloxy) ethyl] trimethyl ammonium chloride.
  • styrene sulfonic acid serves to impart a negative charge to the bare particles
  • [2- (methacryloxy) ethyl] trimethyl ammonium chloride serves to impart a (+) charge to the bare particles.
  • Styrene sulfonic acid or [2- (methacryloxy) ethyl] trimethyl ammonium chloride is very effective in the present invention because it is easy to synthesize particles and can impart an appropriate amount of charge.
  • the external additives of the particles having a (+), (-) charge is one charge
  • the titanium dioxide having the amino group is preferably added to 0.1 to 1 parts by weight, more preferably 0.3 to 0.5 parts by weight based on 100 parts by weight of the second solvent. If it is less than 0.1 part by weight, it is difficult to function as an external additive because it is not sufficiently bonded to bare particles. If it exceeds 1 part by weight, it is an excessive amount, rather the reactivity with particles is lowered, and it is difficult to be externally evenly added to the particles. There is.
  • the external additive is less than 1 part by weight, there is a problem of excessive amount of external additives, etc., relative to the particles, which is not economical, but rather inferior in reactivity with the particles.
  • the external additive is less than the amount to be evenly bonded to the bare particles, there is a problem that the external additive is not sufficiently bonded and the function of the external additive is significantly reduced.
  • the particle surface treatment step (S40) is a step of reacting by adding hydrochloric acid and glutaraldehyde to the reaction preparation solution. This is a particle surface treatment step of effectively binding the external additive to the particles by reacting the external additive with the particles.
  • the particle surface treatment step (S40) it is preferable to add the hydrochloric acid and glutaraldehyde while stirring the reaction preparation solution using a magnetic bar at 10 to 30 °C. That is, it is preferable that reaction temperature is 10-30 degreeC, More preferably, it is effective that it is 20-25 degreeC. In this temperature range, the reaction is maximized, and when it is out of the temperature range, there is a problem that the reaction does not occur, or even when the reaction occurs, the binding force between the particles and the external additives is lowered.
  • the reaction time is preferably 1 to 3 hours, more preferably 2 hours. If less than 1 hour does not occur a sufficient reaction, if more than 3 hours there is a problem that not only the economic efficiency is lowered, but rather the impurities are bonded to the surface of the particles to reduce the durability.
  • the particle surface treatment step (S40) After washing the particles using isopropyl alcohol or ethanol, it is effective to dry at 10 to 30 °C. Although not essential as a process to prevent aggregation or bonding between the particles, washing and drying are more effective.
  • reaction preparation step (S30) a process for preparing the titanium dioxide external additive having the amino group used in the reaction preparation step (S30) must first proceed, and the manufacturing process of the titanium dioxide external additive having such an amino group It consists of a purification step (S10) and an amino group substitution step (S20).
  • the purification step (S10) is a step of purifying titanium dioxide by heat treatment at 300 to 500 °C for 15 to 30 hours. This is a heat treatment process that effectively removes and purifies moisture and impurities in titanium dioxide without damaging titanium dioxide.
  • the heat treatment temperature is preferably 300 to 500 ° C, more preferably 350 to 450 ° C. If the temperature is less than 300 ° C., there is a problem in that the moisture and impurities are not sufficiently purified, and if the temperature exceeds 500 ° C., there is a problem that damage may occur to the titanium dioxide itself.
  • the heat treatment time is preferably 15 to 30 hours, more preferably 20 to 25 hours. If less than 15 hours, there is a problem that can not be sufficiently refined, if more than 30 hours there is a problem that not only economic efficiency, but also damage to titanium dioxide.
  • titanium dioxide is used as the external additive of the particles for electronic paper, since it is white, there is an advantage that the contrast ratio with respect to the white particles can be increased, and it is easy to combine with the electronic paper particles, and the durability is effective as an external additive. to be.
  • the amino group substitution step (S20) is a step of preparing titanium dioxide having an amino group by reacting by adding the titanium dioxide to the first solvent. This is a process for remarkably improving the fluidity of particles and preventing agglomeration by providing amino groups to titanium dioxide.
  • the first solvent does not interfere with the amino group substitution reaction, any solvent that can help, any number of experiments in the present invention, it is most preferable to use toluene. Do.
  • the amino group substitution step (S20) preferably comprises a reaction solution preparation step (S21), heating step (S22), ethoxysilane addition step (S23) and stirring step (S24).
  • the reaction solution preparation step (S21) is a step of preparing the reaction solution by adding and dispersing the titanium dioxide to the first solvent. This is a reaction preparation process in which titanium dioxide is mixed with the first solvent in an optimum amount and then dispersed to facilitate the reaction.
  • the titanium dioxide is preferably added to 20 to 50 parts by weight, more preferably 30 to 40 parts by weight based on 100 parts by weight of the first solvent. to be. If the amount of titanium dioxide is less than 20 parts by weight, the amount contained in the first solvent is too small, there is a problem that the substitution reactivity of the amino group is inferior, if more than 50 parts by weight titanium dioxide is not sufficiently dispersed in the first solvent is effective Not only is the reaction difficult, but there is a problem that a sufficient amino group is not provided to titanium dioxide.
  • the heating step (S22) is a step of heating the reaction solution under a nitrogen atmosphere. This is a process for creating an effective reaction environment for amino group substitution by maintaining a constant high temperature under a nitrogen atmosphere.
  • the temperature of the reaction solution it is preferable to maintain the temperature of the reaction solution at a temperature of 60 °C to 90 °C, more preferably it is effective to maintain a temperature of 70 °C to 80 °C. If it is less than 60 °C there is a problem that the reaction between the nitrogen and the reaction solution is difficult to occur, and if it exceeds 90 °C there is a problem that the reaction solution is difficult to maintain the optimum content ratio due to the high temperature.
  • the ethoxysilane addition step (S23) is a step of adding (3-aminopropyl) triethoxysilane ((3-aminopropyl) triethoxysilane) to the reaction solution. This is a step of adding a reactant of a substitution reaction to give an amino group to titanium dioxide particles.
  • the (3-aminepropyl) triethoxysilane is preferably 20 to 50 parts by weight, more preferably 30 to 40 parts by weight based on 100 parts by weight of the first solvent. Denial is effective. If it is less than 20 parts by weight, there is a problem that a sufficient amino group is difficult to be imparted to the titanium dioxide phase, and if it exceeds 50 parts by weight, it is difficult to uniformly distribute an appropriate amount of the amino groups imparted onto the titanium dioxide, rather the fluidity of the particles is lowered. There is a problem.
  • the stirring step (S24) is a step of stirring the reaction solution. This is a process of reacting (3-aminepropyl) triethoxysilane with titanium dioxide under a nitrogen atmosphere.
  • the reaction solution is preferably stirred for 15 to 30 hours at a temperature of 60 °C to 90 °C, more preferably for 20 to 25 hours at a temperature of 70 °C to 80 °C Is effective. If the temperature is lower than 70 ° C., the temperature is low, and the reactivity decreases, thereby making it difficult to sufficiently bond the amino group to titanium dioxide. If the temperature exceeds 90 ° C., the reaction rate is increased, but the amino group is uniformly bound to the titanium dioxide. It is difficult to achieve, and there is a problem that the reactants are damaged.
  • Drying step (S25) is divided into a step of washing the titanium dioxide having the reaction- terminated amino group with toluene and after washing, the step of sufficiently drying at 15 to 30 °C for 24 to 48 hours. First, by washing, by removing the unreacted material, thereby improving the external reactivity to the particles, and serves to facilitate the subsequent particle surface treatment process through the drying process.
  • the particles for electronic paper using the titanium dioxide external additive prepared according to the present invention as shown in Figure 2, bare particles (Bare particle) 10, and the external additive particles attached to the bare particles (10) (20), and the chemical bond 30 between the external additive particles 20 and the amino group 40 attached to the external additive particles 20.
  • the bare particles 10 are preferably white particles in accordance with the color of the particle external additive for electronic paper using titanium dioxide of the present invention.
  • the charge of the external additive particle 20 is negative (-), and by externally externalizing the external additive particle 20 of the present invention, which bears (-) charge to both the (+) and (-) bare particles 10, Aggregation between particles can be completely prevented.

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Abstract

The present invention relates to a method for surface-treating an electronic paper particle using a titanium dioxide additive, and to the electronic paper particle using the titanium dioxide additive manufactured thereby, and comprises: a reaction preparation step of adding a bare particle to a second solvent into which a titanium dioxide having an amino group is added, and then dispersing same to manufacture a reaction preparation solution; and a particle surface treatment step of adding hydrochloric acid and glutaraldehyde to the reaction preparation solution and reacting same. According to the present invention, by using a solution adsorption method instead of an existing method, the external additive can be more quantitatively and uniformly adsorbed to the particle, and a chemical combination can significantly enhance durability. Also, the durability and mobility of the particles can be significantly enhanced by reacting the hydrochloric acid, the glutaraldehyde, the titanium dioxide having the amino group, and the particles at an optimum proportion according to the solution adsorption method.

Description

이산화티타늄 외첨제를 이용한 전자종이용 입자의 표면처리방법 및 이를 이용하여 제조된 이산화티타늄 외첨제를 이용한 전자종이용 입자 Surface treatment method for electronic paper particles using titanium dioxide external additive and particles for electronic paper using titanium dioxide external additive manufactured using the same
본 발명은 이산화티타늄 외첨제를 이용한 전자종이용 입자의 표면처리방법 및 이를 이용하여 제조된 이산화티타늄 외첨제를 이용한 전자종이용 입자에 관한 것으로, 더욱 상세하게는 종래와 달리, 용액흡착방식을 이용하여, 입자에 외첨제를 화학적으로 흡착시키고, 작용기를 형성시켜 표면처리함으로써, 입자에 강한 전하를 부여하고, 입자간의 뭉침현상을 방지할 뿐만 아니라, 내구성 및 유동성을 현저히 향상시키는 이산화티타늄 외첨제를 이용한 전자종이용 입자의 표면처리방법 및 이를 이용하여 제조된 이산화티타늄 외첨제를 이용한 전자종이용 입자에 관한 것이다.The present invention relates to a surface treatment method for particles of electronic paper using titanium dioxide external additives and to particles for electronic paper using titanium dioxide external additives prepared using the same. More specifically, unlike the conventional method, a solution adsorption method is used. By chemically adsorbing the external additives to the particles, forming functional groups, and surface treating them, the titanium dioxide external additives which not only impart strong charges to the particles and prevent aggregation among the particles, but also significantly improve durability and flowability The present invention relates to a surface treatment method of particles for electronic paper using, and to particles for electronic paper using titanium dioxide external additive prepared using the same.
종래부터 액정표시장치(LCD)를 대체하는 화상표시장치로서, 전기영동방식, 일렉트로크로믹 방식, 서멀 방식, 2색 입자 회전방식 등의 기술을 활용한 전자종이가 제안되어 있다. 이들 종래 기술은 LCD에 비하여 통상의 인쇄물에 가까운 넓은 시야각이 얻어지고, 소비전력이 작으며, 메모리 기능을 가지고 있는 등의 장점으로부터 저렴한 화상표시장치에 사용할 수 있는 기술로 여겨져, 휴대단말용 화상표시, 전자종이 등으로의 전개가 기대되고 있다. BACKGROUND ART Conventionally, as an image display device replacing a liquid crystal display device (LCD), electronic paper using techniques such as an electrophoretic method, an electrochromic method, a thermal method, and a two-color particle rotation method has been proposed. These prior arts are considered to be a technology that can be used in an inexpensive image display device because of the advantages of having a wider viewing angle closer to a normal printed matter, a smaller power consumption, and a memory function than LCDs. , Electronic paper and the like are expected.
이중 전자종이 기술은, 전기장에 의한 마이크로 입자의 빠른 이동을 이용하여, 일정한 공간 내에 부유하는 대전된 입자를 정전기적으로 이동시켜 색을 표시하는 기술로서, 어떠한 극에서든 이동이 일어난 후에는 메모리 효과로 인해 전압을 제거해도 입자들의 위치변화가 없기 때문에 이미지가 사라지지 않아, 마치 종이에 잉크로 인쇄된 것과 같은 효과를 얻을 수 있다. 즉, 자체적인 발광은 하지 않지만, 시각피로도가 대단히 낮아 실제 책을 보는 것과 같은 편안한 감상이 가능하며, 패널의 유연성이 뛰어나, 구부릴 수 있는 정도가 높으며, 그 두께 역시 대단히 얇게 형성할 수 있어 미래형 평판 표시장치 기술로서 큰 기대를 모으고 있다. 또한, 언급한 바와 같이, 한번 표시된 이미지가 패널을 리셋하지 않는 한 오랜 시간 유지되기 때문에 소비전력이 극히 낮아 휴대용 표시장치로서의 활용성이 뛰어나다. 특히, 간단한 공정 및 저가 재료에 의한 낮은 가격은 전자종이의 대중화에 기여할 것으로 예상되고 있다. The dual electronic paper technology uses the rapid movement of microparticles by an electric field to electrostatically move charged particles floating in a certain space to display colors. Therefore, even if the voltage is removed, the image does not disappear because there is no change in the position of the particles, so that the effect as if printed on paper is printed. In other words, it does not emit light by itself, but the visual fatigue is very low, so it is possible to enjoy a comfortable viewing like a real book, and the panel's flexibility is high enough to bend and the thickness can be formed very thin. There is great expectation as a display device technology. In addition, as mentioned, power consumption is extremely low since the displayed image is maintained for a long time unless the panel is reset, thereby making it excellent as a portable display device. In particular, low prices due to simple processes and low cost materials are expected to contribute to the popularization of electronic paper.
일반적으로 사용되고 있는 전자종이 기술로는, 분산입자와 착색용액으로 이루어지는 분산액을 마이크로 캡슐화하여, 이것을 대향하는 기판 사이에 배치하여, 액 속을 입자가 영동하도록 하는 전기영동방식과; 용액을 사용하지 않고, 적어도 일방이 투명한 2장의 기판 사이에 색 및 대전 특성이 다른 2종류 이상의 입자를 봉입하고, 상기 기판의 일방 또는 양방에 형성한 전극으로 이루어지는 전극 쌍으로부터 상기 입자에 전계를 가하고 쿨롱력에 의하여 극성이 다른 대전 입자를 서로 다른 방향으로 비상·이동시켜 화상을 표시하는 충돌 대전 방식이 제안되어 있다.Electronic paper techniques generally used include electrophoretic methods for microencapsulating a dispersion consisting of dispersed particles and a colored solution, and disposing the dispersion liquid between opposing substrates to cause particles to move in the liquid; Without using a solution, two or more kinds of particles having different colors and charging characteristics are enclosed between at least one transparent substrate, and an electric field is applied to the particles from an electrode pair consisting of electrodes formed on one or both of the substrates. A collision charging method has been proposed in which an charged particle having a different polarity is moved and moved in different directions by a Coulomb force to display an image.
상기 전기영동방식과 충돌 대전방식 중 어떠한 방식을 사용하더라도, 유동성 을 갖춘 대전입자(이하 '유동성 입자'라고 한다)의 형성을 위한 기술이 동반되어야 하며, 이러한 유동성 입자는 입자의 표면에 커플링제 등과 같은 외첨제를 코팅함으로써 유동성을 부여하는 구조를 나타낸다.Regardless of which type of electrophoresis method or collision charging method is used, a technique for forming a charged particle having a fluidity (hereinafter referred to as a 'fluid particle') should be accompanied, and the fluid particle may have a coupling agent or the like on the surface of the particle. The structure which gives fluidity | liquidity is shown by coating the same external additive.
상기 유동성 입자는 입자를 포함하는 분산용제에 외첨제를 첨가시켜 믹서 등으로 외첨 혼합(external blending)하는 방식이 사용되고 있다. 이러한 방식에 의한 유동성 입자는, 입자와 외첨제가 물리적으로 결합되는데, 이러한 물리적 결합의 내구성의 한계로 인하여 외첨된 성분이 쉽게 떨어지는 문제점이 있다. The flowable particles include an external blending method using a mixer by adding an external additive to a dispersion solvent containing the particles. The flowable particles in this manner, the particles and the external additives are physically bonded, due to the limitation of the durability of the physical bonds, there is a problem that the external components easily fall off.
이와 같이 외첨제가 쉽게 떨어지면, 대전입자는 동일한 인가 전압에 대하여 충분히 응답할 수 없으며, 대전 특성도 쉽게 변하기 때문에, 화질이 저하되는 문제점이 발생한다. 아울러, 이러한 외첨제 이탈로 인하여 사용시간이 길어질수록 입자 상호 간 응집 발생 확률이 높아지는 문제점이 발생한다.When the external additives fall easily in this way, the charged particles cannot sufficiently respond to the same applied voltage, and the charge characteristics also change easily, resulting in a problem of deterioration in image quality. In addition, the longer the use time due to the departure of the external additive, there is a problem that the probability of occurrence of aggregation between the particles increases.
또한, 물리적 결합이므로, 입자와 외첨제간의 정전기적 인력 등으로 인해, 정량적이고 균일하게 입자와 외첨제간의 결합이 이루어지지 못 하는 문제점이 있다.In addition, since the physical bonding, due to the electrostatic attraction between the particles and the external additive, there is a problem that the binding between the particles and the external additive is not quantitatively and uniformly.
또한, 상기 유동성 입자에 사용되는 고분자 입자의 경우, 유화중합, 분산중합 또는 현탁중합에 따른 중합방법을 이용하는데, 이렇게 제조된 고분자 입자는 대부분 친유성 표면 특성을 나타내기 때문에, 친수성 작용기가 표면에 결합된 고분자 입자를 얻기 위해서는 상기 친수성 작용기의 도입을 위한 새로운 중합방법을 적용하여야 하는 어려움이 있으며, 대부분의 상업화된 친유성 고분자 입자와는 달리, 상기 친수성 작용기가 도입된 고분자 입자를 얻기 위해서는 매우 높은 비용이 소요될 뿐 아니라, 계면 활성제를 활용하는 등 번거롭고, 비경제적인 제조방법을 사용하여야 하는 문제점이 있다.In addition, in the case of the polymer particles used in the flowable particles, a polymerization method according to emulsion polymerization, dispersion polymerization or suspension polymerization is used. Since the polymer particles thus prepared mostly exhibit lipophilic surface properties, hydrophilic functional groups are formed on the surface. It is difficult to apply a new polymerization method for the introduction of the hydrophilic functional group in order to obtain the polymer particles bound, and unlike most commercial lipophilic polymer particles, very high in order to obtain the polymer particles into which the hydrophilic functional groups are introduced. In addition to the cost, there is a problem in that a cumbersome and inexpensive manufacturing method such as using a surfactant is used.
따라서, 유동성 입자의 유동성, 내구성 및 입자뭉침현상 방지 등 다양한 문제를 해결하기 위해, 외첨제 자체를 개질하는 방법으로 이러한 문제를 해결하는 방법의 개발이 요구되고 있을 뿐만 아니라, 유동성 입자에 외첨제를 물리적 결합이 아닌 화학적으로 균일하게 결합시키고, 이러한 결합을 간단하게 구현할 수 있는 입자표면처리공정에 대한 개발이 요구되고 있다. Therefore, in order to solve various problems such as fluidity, durability, and prevention of particle aggregation, it is required to develop a method to solve such problems by modifying the external additive itself, and to apply the external additive to the fluid particles. There is a need for development of a particle surface treatment process that can be chemically uniformly bonded rather than physically bonded and can easily realize such bonding.
본 발명은 상기 문제점을 해결하기 위한 것으로서, 종래와 달리, 용액흡착방식을 이용함으로써, 보다 정량적이고 균일하게 입자에 외첨제를 흡착시킬 수 있을 뿐만 아니라, 화학적 결합에 의하므로, 내구성을 현저히 향상시킬 수 있는 이산화티타늄 외첨제를 이용한 전자종이용 입자의 표면처리방법 및 이를 이용하여 제조된 이산화티타늄 외첨제를 이용한 전자종이용 입자를 제공하는 것을 목적으로 한다.The present invention is to solve the above problems, unlike the prior art, by using a solution adsorption method, not only can adsorb the external additives to the particles more quantitatively and uniformly, but also due to chemical bonding, significantly improve the durability An object of the present invention is to provide a surface treatment method for an electronic paper particle using a titanium dioxide external additive, and an electronic paper particle using a titanium dioxide external additive prepared using the same.
또한, 용액흡착방식으로 염산, 글루타르알테하이드 및 아미노기가 형성된 이산화티타늄과 입자를 최적의 함량비율로 반응시킴으로써, 입자의 내구성 및 유동성을 강화시킨 이산화티타늄 외첨제를 이용한 전자종이용 입자의 표면처리방법 및 이를 이용하여 제조된 이산화티타늄 외첨제를 이용한 전자종이용 입자를 제공하는 것을 목적으로 한다.In addition, the surface treatment of the particles for electronic paper using titanium dioxide external additive which enhances the durability and fluidity of the particles by reacting the titanium dioxide formed with hydrochloric acid, glutaraldehyde and amino groups in the optimum content ratio by the solution adsorption method It is an object of the present invention to provide an electronic paper particle using the method and the titanium dioxide external additive prepared using the same.
또한, 이산화티타늄에 아미노기를 합성함으로써, 입자간 뭉침현상을 억제하고 유동성을 현저히 향상시킬 수 있는 이산화티타늄을 이용한 전자종이용 입자 외첨제의 제조방법 및 이를 이용하여 제조된 이산화티타늄을 이용한 전자종이용 입자 외첨제를 제공하는 것을 목적으로 한다.In addition, by synthesizing an amino group to titanium dioxide, a method of preparing an external particle additive for electronic paper using titanium dioxide that can suppress particle aggregation and significantly improve fluidity, and electronic paper using titanium dioxide prepared using the same It is an object to provide a particle external additive.
뿐만 아니라, 아미노기를 부여한 이산화티타늄을 암모니아수에 반응시켜, 외첨제에 전하를 충분히 부여함으로써, 입자전반에 강한 전하가 형성되고, 이를 통해 입자의 유동성이 증가하고, 입자간 간섭현상을 현저히 감소시킬 수 있는 이산화티타늄을 이용한 전자종이용 입자 외첨제의 제조방법 및 이를 이용하여 제조된 이산화티타늄을 이용한 전자종이용 입자 외첨제를 제공하는 것을 목적으로 한다.In addition, by reacting titanium dioxide given an amino group with ammonia water and giving sufficient charge to the external additive, a strong charge is formed throughout the particles, thereby increasing the fluidity of the particles and significantly reducing the inter-particle interference phenomenon. It is an object of the present invention to provide a method for producing an electronic paper particle additive using titanium dioxide and an electronic paper particle additive using titanium dioxide prepared using the same.
또한, 최적의 물질 및 그 함량을 통해 외첨제를 효과적으로 제조함으로써, 간단하면서도 경제적으로 화학적 결합 형성이 가능하며, 특히, 외첨제가 백색입자의 색상을 오히려 강화함으로써, 전자종이장치에서의 콘트라스트비를 향상시킬 수 있는 이산화티타늄을 이용한 전자종이용 입자 외첨제의 제조방법 및 이를 이용하여 제조된 이산화티타늄을 이용한 전자종이용 입자 외첨제를 제공하는 것을 목적으로 한다.In addition, by effectively preparing the external additive through the optimal material and its content, it is possible to form chemical bonds simply and economically, and in particular, by increasing the color of the white particles, the external additive improves the contrast ratio in the electronic paper apparatus. An object of the present invention is to provide an electronic paper particle additive for electronic paper using titanium dioxide and an electronic paper particle additive for titanium paper prepared using the same.
상기와 같은 목적을 달성하기 위한 본 발명에 따른 이산화티타늄 외첨제를 이용한 전자종이용 입자의 표면처리방법은, 아미노기를 갖는 이산화티타늄을 첨가한 제 2용매에 베어입자를 첨가한 후, 분산시켜 반응준비용액을 제조하는 반응준비단계; 및 상기 반응준비용액에 염산 및 글루타르알테하이드를 첨가하여 반응시키는 입자표면처리단계;를 포함하여 이루어지는 것을 특징으로 한다.In order to achieve the above object, the surface treatment method of the particle for electronic paper using the titanium dioxide external additive according to the present invention comprises adding bare particles to a second solvent to which titanium dioxide having an amino group is added, followed by dispersion and reaction. A reaction preparation step of preparing a preparation solution; And a particle surface treatment step of adding and reacting hydrochloric acid and glutaraldehyde to the reaction preparation solution.
상기 반응준비단계에서, 상기 아미노기를 갖는 이산화티타늄은, 이산화티타늄을 300 내지 500℃에서 15 내지 30시간동안 열처리하여 정제시키는 정제단계; 및제 1용매에 상기 이산화티타늄을 첨가하여 반응시켜 아미노기를 갖는 이산화티타늄을 제조하는 아미노기치환단계;를 통해 제조되는 것을 특징으로 한다.In the reaction preparation step, the titanium dioxide having the amino group, the purification step of purifying the titanium dioxide by heat treatment at 300 to 500 ℃ for 15 to 30 hours; And an amino group substitution step of adding titanium dioxide to the first solvent and reacting to produce titanium dioxide having an amino group.
또한, 상기 반응준비단계에서, 상기 제 2용매는 이소프로필 알코올(Isopropyl Alcohol)인 것을 특징으로 하며, 상기 반응준비단계에서, 상기 베어입자는, 모노머, 중합개시제 및 이온성모노머를 합성하여 제조되며, 상기 이온성 모노머는 스티렌설폰산(Styrene sulfonic acid) 또는 [2-(메타크릴옥시)에틸]트리메틸 암모늄 클로라이드 중 어느 하나인 것을 특징으로 한다.In addition, in the reaction preparation step, the second solvent is characterized in that the isopropyl alcohol (Isopropyl Alcohol), in the reaction preparation step, the bare particles are prepared by synthesizing a monomer, a polymerization initiator and an ionic monomer. , The ionic monomer is characterized in that any one of styrene sulfonic acid (Styrene sulfonic acid) or [2- (methacryloxy) ethyl] trimethyl ammonium chloride.
상기 모노머는 메틸메타크릴레이트, 에틸렌테레프탈레이트, 스티렌술포네이트, 비닐아세트테이트, 메틸스티렌, 아크릴산, 부틸메타크릴레이트, 에틸메타크릴레이트, 2-에틸헥실아크릴레이트 또는 N-비닐카프로락탐 중 적어도 하나이며, 상기 중합개시제는 퍼옥시드화합물 또는 아조화합물 중 적어도 하나인 것을 특징으로 한다.The monomer is at least one of methyl methacrylate, ethylene terephthalate, styrenesulfonate, vinyl acetate, methyl styrene, acrylic acid, butyl methacrylate, ethyl methacrylate, 2-ethylhexyl acrylate or N-vinyl caprolactam Wherein the polymerization initiator is at least one of a peroxide compound or an azo compound.
또한, 상기 반응준비단계에서, 상기 제 2용매 100중량부에 대하여, 상기 아미노기를 갖는 이산화티타늄은 0.1 내지 1중량부를 첨가하는 것을 특징으로 하며, 상기 제 2용매 100중량부에 대하여, 상기 베어입자는 1 내지 5중량부를 첨가하는 것을 특징으로 한다.Further, in the reaction preparation step, the titanium dioxide having the amino group is added to 0.1 parts by weight based on 100 parts by weight of the second solvent, with respect to 100 parts by weight of the second solvent, the bare particles Is characterized by adding 1 to 5 parts by weight.
상기 입자표면처리단계에서, 상기 제 2용매 100중량부에 대하여, 상기 염산 및 글루타르알테하이드는 각각 60 내지 90중량부를 첨가하는 것을 특징으로 하며,상기 입자표면처리단계는, 상기 반응준비용액을 10 내지 30℃에서 마그네틱바를 사용하여 교반하면서, 상기 염산 및 글루타르알테하이드를 첨가하는 것을 특징으로 한다.In the particle surface treatment step, the hydrochloric acid and glutaraldehyde are added to 60 parts by weight to 90 parts by weight, respectively, with respect to 100 parts by weight of the second solvent. The hydrochloric acid and glutaraldehyde are added while stirring using a magnetic bar at 10 to 30 ° C.
또한, 상기 입자표면처리단계에서, 반응시간은 1 내지 3시간인 것을 특징으로 하며, 상기 아미노기치환단계에서, 상기 제 1용매는 톨루엔인 것을 특징으로 한다.In addition, in the particle surface treatment step, the reaction time is characterized in that 1 to 3 hours, in the amino group substitution step, the first solvent is characterized in that toluene.
상기 아미노기치환단계는, 상기 제 1용매에 상기 이산화티타늄을 첨가한 후, 분산시켜 반응용액을 제조하는 반응용액 제조단계; 상기 반응용액을 질소분위기하에서 가열하는 가열단계; 상기 반응용액에 (3-아민프로필)트리에톡시실란((3-aminopropyl) triethoxysilane)을 첨가하는 에톡시실란 첨가단계; 및 상기 반응용액을 교반시키는 교반단계;를 포함하여 이루어지는 것을 특징으로 한다.The amino group substitution step, the reaction solution manufacturing step of preparing a reaction solution by adding the titanium dioxide to the first solvent, and then dispersing; A heating step of heating the reaction solution under a nitrogen atmosphere; An ethoxysilane addition step of adding (3-aminopropyl) triethoxysilane to the reaction solution; And a stirring step of stirring the reaction solution.
또한, 상기 반응용액 제조단계에서, 상기 제 1용매 100중량부에 대하여, 상기 이산화티타늄은 20 내지 50중량부인 것을 특징으로 하며, 상기 가열단계는, 상기 반응용액의 온도를 60℃ 내지 90℃의 온도로 유지시키는 것을 특징으로 한다.In addition, in the reaction solution manufacturing step, the titanium dioxide is characterized in that 20 to 50 parts by weight with respect to 100 parts by weight of the first solvent, the heating step, the temperature of the reaction solution of 60 ℃ to 90 ℃ It is characterized by maintaining at a temperature.
상기 에톡시실란첨가단계에서, 상기 제 1용매 100중량부에 대하여, 상기 (3-아민프로필)트리에톡시실란은 20 내지 50중량부인 것을 특징으로 하며, 상기 교반단계는, 상기 반응용액을 60℃ 내지 90℃의 온도하에서 15 내지 30시간동안 교반시키는 것을 특징으로 한다.In the ethoxysilane addition step, based on 100 parts by weight of the first solvent, the (3-aminepropyl) triethoxysilane is characterized in that 20 to 50 parts by weight, the stirring step, the reaction solution 60 It is characterized by stirring for 15 to 30 hours at a temperature of ℃ to 90 ℃.
본 발명의 이산화티타늄 외첨제를 이용한 전자종이용 입자의 표면처리방법 및 이를 이용하여 제조된 이산화티타늄 외첨제를 이용한 전자종이용 입자에 따르면, 종래와 달리, 용액흡착방식을 이용함으로써, 보다 정량적이고 균일하게 입자에 외첨제를 흡착시킬 수 있을 뿐만 아니라, 화학적 결합에 의하므로, 내구성을 현저히 향상시킬 수 있는 장점이 있다.According to the surface treatment method of the particle for electronic paper using the titanium dioxide external additive of the present invention and the particle for electronic paper using the titanium dioxide external additive prepared by using the same, unlike the conventional method, by using a solution adsorption method, Not only can the external additive be adsorbed to the particles uniformly, but also due to the chemical bonding, the durability can be significantly improved.
또한, 용액흡착방식으로 염산, 글루타르알테하이드 및 아미노기가 형성된 이산화티타늄과 입자를 최적의 함량비율로 반응시킴으로써, 입자의 내구성 및 유동성을 현저히 향상시킬 수 있는 장점이 있다. In addition, by reacting the titanium dioxide and the particles formed with hydrochloric acid, glutaraldehyde and amino groups in an optimum content ratio in a solution adsorption method, there is an advantage that can significantly improve the durability and flowability of the particles.
또한, 이산화티타늄에 아미노기를 합성함으로써, 입자간 뭉침현상을 억제하고 유동성을 현저히 향상시킬 수 있는 장점이 있다.In addition, by synthesizing the amino group in titanium dioxide, there is an advantage that can suppress the aggregation between particles and significantly improve the fluidity.
뿐만 아니라, 아미노기를 부여한 이산화티타늄을 암모니아수에 반응시켜, 외첨제에 전하를 충분히 부여함으로써, 입자전반에 강한 전하가 형성되고, 이를 통해 입자의 유동성이 증가하고, 입자간 간섭현상을 현저히 감소시킬 수 있는 장점이 있다.In addition, by reacting titanium dioxide given an amino group with ammonia water and giving sufficient charge to the external additive, a strong charge is formed throughout the particles, thereby increasing the fluidity of the particles and significantly reducing the inter-particle interference phenomenon. There is an advantage.
또한, 최적의 물질 및 그 함량을 통해 외첨제를 효과적으로 제조함으로써, 간단하면서도 경제적으로 화학적 결합 형성이 가능하며, 특히, 외첨제가 백색입자의 색상을 오히려 강화함으로써, 전자종이장치에서의 콘트라스트비를 향상시킬 수 있는 장점이 있다.In addition, by effectively preparing the external additive through the optimal material and its content, it is possible to form chemical bonds simply and economically, and in particular, by increasing the color of the white particles, the external additive improves the contrast ratio in the electronic paper apparatus. There is an advantage to this.
도 1은 본 발명에 따른 이산화티타늄을 이용한 전자종이용 입자 외첨제의 제조방법을 순차적으로 나타낸 순서도1 is a flow chart sequentially showing a manufacturing method of the particle external additive for electronic paper using titanium dioxide according to the present invention.
도 2는 본 발명에 따른 이산화티타늄 외첨제를 이용한 전자종이용 입자의 표면처리방법을 이용하여 제조된 이산화티타늄 외첨제를 이용한 전자종이용 입자를 나타낸 단면도Figure 2 is a cross-sectional view showing the particles for electronic paper using the titanium dioxide external additive prepared by using the surface treatment method of the electronic paper particles using the titanium dioxide external additive according to the present invention.
이하, 본 발명에 의한 이산화티타늄 외첨제를 이용한 전자종이용 입자의 표면처리방법 및 이를 이용하여 제조된 이산화티타늄 외첨제를 이용한 전자종이용 입자에 대하여 본 발명의 바람직한 하나의 실시형태를 첨부된 도면을 참조하여 상세히 설명한다. 본 발명은 하기의 실시예에 의하여 보다 더 잘 이해될 수 있으며, 하기의 실시예는 본 발명의 예시목적을 위한 것이고, 첨부된 특허청구범위에 의하여 한정되는 보호범위를 제한하고자 하는 것은 아니다.Hereinafter, a preferred embodiment of the present invention with respect to the surface treatment method of the particle for electronic paper using the titanium dioxide external additive according to the present invention and the particle for electronic paper using the titanium dioxide external additive prepared by using the same. It will be described in detail with reference to. The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.
도 1에 나타난 바와 같이, 본 발명에 의한 이산화티타늄 외첨제를 이용한 전자종이용 입자의 표면처리방법은, 정제단계(S10), 아미노기치환단계(S20), 반응준비단계(S30) 및 입자표면처리단계(S40)를 포함하여 이루어지는 것을 특징으로 한다.As shown in Figure 1, the surface treatment method of the electronic paper particles using the titanium dioxide external additive according to the present invention, the purification step (S10), amino-substituted step (S20), reaction preparation step (S30) and particle surface treatment It characterized in that it comprises a step (S40).
먼저, 반응준비단계(S30)는 아미노기를 갖는 이산화티타늄을 첨가한 제 2용매에 베어입자를 첨가한 후, 분산시켜 반응준비용액을 제조하는 단계이다. 이는 입자표면처리 반응개시전에, 베어입자와 외첨제를 용매에 분산시켜 반응을 준비하는 공정이다.First, the reaction preparation step (S30) is a step of preparing a reaction preparation solution by adding the bare particles to the second solvent to which titanium dioxide having an amino group is added, and then dispersed. This is a step of preparing a reaction by dispersing bare particles and an external additive in a solvent before starting the particle surface treatment reaction.
상기 반응준비단계(S30)에서, 상기 제 2용매는 이산화티타늄 외첨제와 베어입자의 분산을 용이하게 하고, 이후 입자표면처리반응을 도울 수 있는 용매이면 어느 것이든 무방하나, 수차례의 실험결과, 본 발명에서는 이소프로필 알코올(Isopropyl Alcohol)을 사용하는 것이 가장 효과적인 바, 이를 사용하는 것이 바람직하다.In the reaction preparation step (S30), the second solvent may be any solvent that facilitates the dispersion of the titanium dioxide external additive and the bare particles, and may help the particle surface treatment reaction thereafter, but several experiment results In the present invention, it is most effective to use isopropyl alcohol, which is preferably used.
또한, 상기 반응준비단계(S30)에서, 상기 베어입자는, 모노머, 중합개시제 및 이온성모노머를 합성하여 제조되는 것이 바람직하다. In addition, in the reaction preparation step (S30), the bare particles are preferably prepared by synthesizing a monomer, a polymerization initiator and an ionic monomer.
즉, 베어입자의 제조방법은, 용매에 모노머와 중합개시제, 그리고 이온성모노머를 투입하여 교반함으로써, 반응시켜, 베어입자를 합성시키는 것이 바람직하다.That is, in the method for producing the bare particles, it is preferable that the monomers, the polymerization initiator, and the ionic monomer are added to the solvent, followed by stirring to synthesize the bare particles.
여기서, 상기 용매는 입자합성에 방해되지 않고, 반응을 도울 수 있는 물질이면 어느 것이든 무방하나, 메탄올을 사용하는 것이 가장 바람직하다. Herein, the solvent may be any material that does not interfere with particle synthesis and may help the reaction, but methanol is most preferably used.
또한, 상기 모노머는 메틸메타크릴레이트, 에틸렌테레프탈레이트, 스티렌술포네이트, 비닐아세트테이트, 메틸스티렌, 아크릴산, 부틸메타크릴레이트, 에틸메타크릴레이트, 2-에틸헥실아크릴레이트 또는 N-비닐카프로락탐 중 적어도 하나를 사용하는 것이 바람직하며, 상기 물질들을 공중합하여 사용할 수도 있다. In addition, the monomer is methyl methacrylate, ethylene terephthalate, styrene sulfonate, vinyl acetate, methyl styrene, acrylic acid, butyl methacrylate, ethyl methacrylate, 2-ethylhexyl acrylate or N-vinyl caprolactam It is preferable to use at least one, and the above materials may be copolymerized.
상기 중합개시제는 무유화 중합을 촉발할 수 있는 모든 자유 라디칼 중합 개시제를 사용할 수 있으나, 본 발명에서는 퍼옥시드화합물 또는 아조화합물 중 적어도 하나인 것이 바람직하며, 상기 퍼옥시드화합물은 원칙적으로 무기 퍼옥시드, 예컨대 알킬 하이드로퍼옥시드일 수 있고, 예로는 tert-부틸, p-멘틸 및 쿠밀 하이드로퍼옥시더, 및 또한 디알킬 또는 디아릴 퍼옥시드, 예컨대 di-tert-부틸 퍼옥시드 또는 디쿠밀 퍼옥시드가 있으며, 아조화합물로는 주로 2,2‘-아조비스(이소부틸로니트릴), 2,2’-아조비스(아이소부티라미딘) 하이드로클로라이드(2,2‘-azobis(isobutyramidine)hydrochloride)(이하 'AIBN'라 한다)를 중합개시제로 사용하는 것이 가장 효율적이다.The polymerization initiator may use any free radical polymerization initiator capable of triggering an emulsion-free polymerization, but in the present invention, at least one of a peroxide compound or an azo compound is preferable, and the peroxide compound is, in principle, an inorganic peroxide, For example alkyl hydroperoxides, examples being tert-butyl, p-mentyl and cumyl hydroperoxide, and also dialkyl or diaryl peroxides such as di-tert-butyl peroxide or dicumyl peroxide Azo compounds are mainly 2,2'-azobis (isobutylonitrile), 2,2'-azobis (isobutyramidine) hydrochloride (2,2'-azobis (isobutyramidine) hydrochloride) It is most efficient to use 'AIBN') as a polymerization initiator.
또한, 상기 이온성 모노머는 스티렌설폰산(Styrene sulfonic acid) 또는 [2-(메타크릴옥시)에틸]트리메틸 암모늄 클로라이드 중 어느 하나인 것이 바람직하다. 여기서, 스티렌설폰산은 베어입자에 (-)전하를 부여하는 역할을 하며, [2-(메타크릴옥시)에틸]트리메틸 암모늄 클로라이드는 베어입자에 (+)전하를 부여하는 역할을 한다. 스티렌설폰산(Styrene sulfonic acid) 또는 [2-(메타크릴옥시)에틸]트리메틸 암모늄 클로라이드는 본 발명에서 입자합성이 용이하면서도 적절한 양의 전하를 부여할 수 있어 매우 효과적이다. In addition, the ionic monomer is preferably either styrene sulfonic acid or [2- (methacryloxy) ethyl] trimethyl ammonium chloride. Here, styrene sulfonic acid serves to impart a negative charge to the bare particles, and [2- (methacryloxy) ethyl] trimethyl ammonium chloride serves to impart a (+) charge to the bare particles. Styrene sulfonic acid or [2- (methacryloxy) ethyl] trimethyl ammonium chloride is very effective in the present invention because it is easy to synthesize particles and can impart an appropriate amount of charge.
또한, 본 발명에서는 입자에 전하를 부여함으로써, 외첨제에 부여된 전하와 함께 강한 전하를 통해, 입자의 유동성을 강화시키고, (+),(-)전하를 갖는 입자의 외첨제는 하나의 전하로 통일함으로써, 입자의 뭉침현상을 방지하는 효과가 있다.In addition, in the present invention, by imparting a charge to the particles, through the strong charges along with the charges to the external additives to enhance the fluidity of the particles, the external additives of the particles having a (+), (-) charge is one charge By integrating with, it is effective to prevent agglomeration of particles.
상기 반응준비단계(S30)에서, 상기 제 2용매 100중량부에 대하여, 상기 아미노기를 갖는 이산화티타늄은 0.1 내지 1중량부를 첨가하는 것이 바람직하며, 더욱 바람직하게는 0.3 내지 0.5중량부인 것이 효과적이다. 0.1중량부 미만인 경우에는 베어입자에 충분히 결합되지 않아 외첨제로서 기능하기 어려운 문제가 있으며, 1중량부를 초과하는 경우에는 과다한 양으로, 오히려 입자와의 반응성이 저하되고, 입자에 고르게 외첨되기 어려운 문제가 있다.In the reaction preparation step (S30), the titanium dioxide having the amino group is preferably added to 0.1 to 1 parts by weight, more preferably 0.3 to 0.5 parts by weight based on 100 parts by weight of the second solvent. If it is less than 0.1 part by weight, it is difficult to function as an external additive because it is not sufficiently bonded to bare particles. If it exceeds 1 part by weight, it is an excessive amount, rather the reactivity with particles is lowered, and it is difficult to be externally evenly added to the particles. There is.
또한, 상기 제 2용매 100중량부에 대하여, 상기 베어입자는 1 내지 5중량부를 첨가하는 것이 바람직하며, 더욱 바람직하게는 2 내지 3중량부인 것이 효과적이다. 1중량부 미만인 경우에는 입자 대비 외첨제 등의 물질이 과다하여, 비경제적일 뿐만 아니라, 오히려 입자와의 반응성이 떨어지는 문제가 있으며, 5중량부를 초과하는 경우에는 외첨제 대비 입자의 양이 과도하게 많아, 외첨제가 베어입자에 고르게 결합될만큼의 양보다 적어, 충분히 외첨제가 결합되지 않아 외첨제의 기능이 현저히 저하되는 문제가 있다. In addition, it is preferable to add 1 to 5 parts by weight, more preferably 2 to 3 parts by weight, based on 100 parts by weight of the second solvent. If it is less than 1 part by weight, there is a problem of excessive amount of external additives, etc., relative to the particles, which is not economical, but rather inferior in reactivity with the particles. In many cases, the external additive is less than the amount to be evenly bonded to the bare particles, there is a problem that the external additive is not sufficiently bonded and the function of the external additive is significantly reduced.
다음으로, 입자표면처리단계(S40)는 상기 반응준비용액에 염산 및 글루타르알테하이드를 첨가하여 반응시키는 단계이다. 이는 외첨제와 입자를 반응시킴으로써, 입자에 외첨제를 효과적으로 결합시키는 입자 표면처리공정이다.Next, the particle surface treatment step (S40) is a step of reacting by adding hydrochloric acid and glutaraldehyde to the reaction preparation solution. This is a particle surface treatment step of effectively binding the external additive to the particles by reacting the external additive with the particles.
상기 입자표면처리단계(S40)에서, 염산 및 글루타르알테하이드는 반응성을 높여주는 역할을 한다. 이는 두 물질을 모두 첨가해야 비로소 반응이 진행된다.In the particle surface treatment step (S40), hydrochloric acid and glutaraldehyde serve to increase the reactivity. It is only after the addition of both materials that the reaction proceeds.
상기 제 2용매 100중량부에 대하여, 상기 염산 및 글루타르알테하이드는 각각 60 내지 90중량부를 첨가하는 것이 바람직하며, 더욱 바람직하게는 70 내지 80중량부를 첨가하는 것이 효과적이다. 60중량부 미만인 경우에는 입자에 외첨제가 결합하는 반응이 거의 일어나지 못 하는 문제가 있으며, 90중량부를 초과하는 경우에는 반응속도는 급격하게 빨라지나, 입자표면에 외첨제가 고르게 결합하지 못 하며, 결합력 또한 현저히 저하되는 문제가 있다. It is preferable to add 60-90 weight part of said hydrochloric acid and glutaraldehyde each with respect to 100 weight part of said 2nd solvents, More preferably, it is effective to add 70-80 weight part. If it is less than 60 parts by weight, there is a problem in that the reaction of binding the external additive to the particles hardly occurs. If it exceeds 90 parts by weight, the reaction rate is rapidly increased, but the external additive is not evenly bound to the particle surface, and the binding force is also high. There is a problem that is significantly reduced.
또한, 상기 입자표면처리단계(S40)는, 상기 반응준비용액을 10 내지 30℃에서 마그네틱바를 사용하여 교반하면서, 상기 염산 및 글루타르알테하이드를 첨가하는 것이 바람직하다. 즉, 반응온도는 10 내지 30℃인 것이 바람직하며, 더욱 바람직하게는 20 내지 25℃인 것이 효과적이다. 이러한 온도범위 내에서 반응이 극대화되며, 상기 온도범위를 벗어나는 경우에는 반응이 일어나지 않거나, 반응이 일어나더라도 입자와 외첨제와의 결합력이 저하되는 문제가 있다. In addition, the particle surface treatment step (S40), it is preferable to add the hydrochloric acid and glutaraldehyde while stirring the reaction preparation solution using a magnetic bar at 10 to 30 ℃. That is, it is preferable that reaction temperature is 10-30 degreeC, More preferably, it is effective that it is 20-25 degreeC. In this temperature range, the reaction is maximized, and when it is out of the temperature range, there is a problem that the reaction does not occur, or even when the reaction occurs, the binding force between the particles and the external additives is lowered.
또한, 반응시간은 1 내지 3시간인 것이 바람직하며, 더욱 바람직하게는 2시간인 것이 효과적이다. 1시간 미만인 경우에는 충분한 반응이 일어나지 못 하며, 3시간을 초과하는 경우에는 경제성이 떨어질 뿐만 아니라, 오히려 입자표면에 불순물이 결합하여 내구성이 저하되는 문제가 있다. The reaction time is preferably 1 to 3 hours, more preferably 2 hours. If less than 1 hour does not occur a sufficient reaction, if more than 3 hours there is a problem that not only the economic efficiency is lowered, but rather the impurities are bonded to the surface of the particles to reduce the durability.
입자표면처리단계(S40) 후에는, 이소프로필 알코올 또는 에탄올을 사용하여 입자를 세척한 후에, 10 내지 30℃에서 건조시키는 것이 효과적이다. 입자간의 뭉침이나 결합을 방지하기 위한 과정으로 필수적이지는 않지만, 세척 및 건조하는 것이 보다 효과적이다.After the particle surface treatment step (S40), after washing the particles using isopropyl alcohol or ethanol, it is effective to dry at 10 to 30 ℃. Although not essential as a process to prevent aggregation or bonding between the particles, washing and drying are more effective.
상기 반응준비단계(S30)를 위해, 반응준비단계(S30)에서 사용되는 상기 아미노기를 갖는 이산화티타늄 외첨제를 제조하기 위한 과정이 먼저 진행되어야 하며, 이러한 아미노기를 갖는 이산화티타늄 외첨제의 제조과정은 정제단계(S10) 및 아미노기치환단계(S20)로 이루어진다.For the reaction preparation step (S30), a process for preparing the titanium dioxide external additive having the amino group used in the reaction preparation step (S30) must first proceed, and the manufacturing process of the titanium dioxide external additive having such an amino group It consists of a purification step (S10) and an amino group substitution step (S20).
상기 정제단계(S10)는 이산화티타늄을 300 내지 500℃에서 15 내지 30시간동안 열처리하여 정제시키는 단계이다. 이는 이산화티타늄 내의 수분과 불순물을 이산화티타늄의 손상없이 효과적으로 제거하여 정제하는 열처리공정이다.The purification step (S10) is a step of purifying titanium dioxide by heat treatment at 300 to 500 ℃ for 15 to 30 hours. This is a heat treatment process that effectively removes and purifies moisture and impurities in titanium dioxide without damaging titanium dioxide.
또한, 열처리온도는 300 내지 500℃인 것이 바람직하며, 더욱 바람직하게는 350 내지 450℃인 것이 효과적이다. 300℃미만인 경우에는 수분 및 불순물이 충분히 정제되지 못 하는 문제가 있으며, 500℃를 초과하는 경우에는 이산화티타늄 자체에 손상이 발생할 수 있는 문제가 있다. In addition, the heat treatment temperature is preferably 300 to 500 ° C, more preferably 350 to 450 ° C. If the temperature is less than 300 ° C., there is a problem in that the moisture and impurities are not sufficiently purified, and if the temperature exceeds 500 ° C., there is a problem that damage may occur to the titanium dioxide itself.
열처리시간은 15 내지 30시간인 것이 바람직하며, 더욱 바람직하게는 20 내지 25시간인 것이 효과적이다. 15시간 미만인 경우에는 충분히 정제되지 못 하는 문제가 있으며, 30시간을 초과하는 경우에는 경제성이 떨어질 뿐만 아니라, 이산화티타늄에 손상이 발생할 수 있는 문제가 있다.The heat treatment time is preferably 15 to 30 hours, more preferably 20 to 25 hours. If less than 15 hours, there is a problem that can not be sufficiently refined, if more than 30 hours there is a problem that not only economic efficiency, but also damage to titanium dioxide.
여기서, 이산화티타늄을 전자종이용 입자의 외첨제로 사용함으로써, 백색이므로, 백색입자에 대한 콘트라스트비를 높일 수 있는 장점이 있으며, 전자종이용 입자와의 결합이 용이하고, 내구성이 강하여 외첨제로써 효과적이다.Here, since titanium dioxide is used as the external additive of the particles for electronic paper, since it is white, there is an advantage that the contrast ratio with respect to the white particles can be increased, and it is easy to combine with the electronic paper particles, and the durability is effective as an external additive. to be.
다음으로, 아미노기치환단계(S20)는 제 1용매에 상기 이산화티타늄을 첨가하여 반응시켜 아미노기를 갖는 이산화티타늄을 제조하는 단계이다. 이는 이산화티타늄에 아미노기를 부여함으로써, 입자의 유동성을 현저히 향상시키고, 뭉침현상을 방지하기 위한 공정이다.Next, the amino group substitution step (S20) is a step of preparing titanium dioxide having an amino group by reacting by adding the titanium dioxide to the first solvent. This is a process for remarkably improving the fluidity of particles and preventing agglomeration by providing amino groups to titanium dioxide.
상기 아미노기치환단계(S20)에서, 상기 제 1용매는 아미노기치환반응을 방해하지 않고, 도움을 줄 수 있는 용매이면 어느 것이든 무방하나, 본 발명에서는 수차례 실험결과, 톨루엔을 사용하는 것이 가장 바람직하다. In the amino group substitution step (S20), the first solvent does not interfere with the amino group substitution reaction, any solvent that can help, any number of experiments in the present invention, it is most preferable to use toluene. Do.
또한, 상기 아미노기치환단계(S20)는, 반응용액 제조단계(S21), 가열단계(S22), 에톡시실란 첨가단계(S23) 및 교반단계(S24)를 포함하여 이루어지는 것이 바람직하다.In addition, the amino group substitution step (S20), preferably comprises a reaction solution preparation step (S21), heating step (S22), ethoxysilane addition step (S23) and stirring step (S24).
먼저, 반응용액 제조단계(S21)는 상기 제 1용매에 상기 이산화티타늄을 첨가한 후, 분산시켜 반응용액을 제조하는 단계이다. 이는 제 1용매에 이산화티타늄을 최적의 양으로 혼합한 후, 분산시켜 반응을 용이하게 하는 반응준비공정이다. First, the reaction solution preparation step (S21) is a step of preparing the reaction solution by adding and dispersing the titanium dioxide to the first solvent. This is a reaction preparation process in which titanium dioxide is mixed with the first solvent in an optimum amount and then dispersed to facilitate the reaction.
상기 반응용액 제조단계(S21)에서, 상기 제 1제 1용매 100중량부에 대하여, 상기 이산화티타늄은 20 내지 50중량부를 첨가하는 것이 바람직하며, 더욱 바람직하게는 30 내지 40중량부를 첨가하는 것이 효과적이다. 이산화티타늄이 20중량부 미만인 경우에는 제 1용매내에 함유된 양이 너무 적어, 이후 아미노기의 치환반응성이 떨어지는 문제가 있으며, 50중량부를 초과하는 경우에는 제 1용매내에 이산화티타늄이 충분히 분산되지 않아 효과적인 반응이 어려울 뿐만 아니라, 이산화티타늄에 충분한 아미노기가 부여되기 어려운 문제가 있다.In the reaction solution preparation step (S21), the titanium dioxide is preferably added to 20 to 50 parts by weight, more preferably 30 to 40 parts by weight based on 100 parts by weight of the first solvent. to be. If the amount of titanium dioxide is less than 20 parts by weight, the amount contained in the first solvent is too small, there is a problem that the substitution reactivity of the amino group is inferior, if more than 50 parts by weight titanium dioxide is not sufficiently dispersed in the first solvent is effective Not only is the reaction difficult, but there is a problem that a sufficient amino group is not provided to titanium dioxide.
다음으로, 가열단계(S22)는 상기 반응용액을 질소분위기하에서 가열하는 단계이다. 이는 질소분위기하에서 높은 온도를 일정하게 유지함으로써, 아미노기치환에 효과적인 반응환경을 조성하는 공정이다.Next, the heating step (S22) is a step of heating the reaction solution under a nitrogen atmosphere. This is a process for creating an effective reaction environment for amino group substitution by maintaining a constant high temperature under a nitrogen atmosphere.
상기 가열단계(S22)는, 상기 반응용액의 온도를 60℃ 내지 90℃의 온도로 유지시키는 것이 바람직하며, 더욱 바람직하게는 70℃ 내지 80℃의 온도로 유지시키는 것이 효과적이다. 60℃미만인 경우에는 질소와 반응용액간의 반응이 일어나기 어려운 문제가 있으며, 90℃를 초과하는 경우에는 고온으로 인해 반응용액이 증발하여 최적의 함량비율을 유지하기 어려운 문제가 있다.In the heating step (S22), it is preferable to maintain the temperature of the reaction solution at a temperature of 60 ℃ to 90 ℃, more preferably it is effective to maintain a temperature of 70 ℃ to 80 ℃. If it is less than 60 ℃ there is a problem that the reaction between the nitrogen and the reaction solution is difficult to occur, and if it exceeds 90 ℃ there is a problem that the reaction solution is difficult to maintain the optimum content ratio due to the high temperature.
또한, 에톡시실란 첨가단계(S23)는 상기 반응용액에 (3-아민프로필)트리에톡시실란((3-aminopropyl) triethoxysilane)을 첨가하는 단계이다. 이는 아미노기를 이산화티타늄입자에 부여하기 위해, 치환반응의 반응물질을 투입하는 공정이다.In addition, the ethoxysilane addition step (S23) is a step of adding (3-aminopropyl) triethoxysilane ((3-aminopropyl) triethoxysilane) to the reaction solution. This is a step of adding a reactant of a substitution reaction to give an amino group to titanium dioxide particles.
상기 에톡시실란첨가단계(S23)에서, 상기 제 1용매 100중량부에 대하여, 상기 (3-아민프로필)트리에톡시실란은 20 내지 50중량부인 것이 바람직하며, 더욱 바람직하게는 30 내지 40중량부인 것이 효과적이다. 20중량부 미만인 경우에는 충분한 아미노기가 이산화티타늄상에 부여되기 어려운 문제가 있으며, 50중량부를 초과하는 경우에는 이산화티타늄상에 부여된 아미노기가 균일하게 적절한 양이 분포되기 어려워, 오히려 입자의 유동성이 저하되는 문제가 있다.In the ethoxysilane addition step (S23), the (3-aminepropyl) triethoxysilane is preferably 20 to 50 parts by weight, more preferably 30 to 40 parts by weight based on 100 parts by weight of the first solvent. Denial is effective. If it is less than 20 parts by weight, there is a problem that a sufficient amino group is difficult to be imparted to the titanium dioxide phase, and if it exceeds 50 parts by weight, it is difficult to uniformly distribute an appropriate amount of the amino groups imparted onto the titanium dioxide, rather the fluidity of the particles is lowered. There is a problem.
마지막으로, 교반단계(S24)는 상기 반응용액을 교반시키는 단계이다. 이는 질소분위기하에서 (3-아민프로필)트리에톡시실란과 이산화티타늄을 반응시키는 공정이다.Finally, the stirring step (S24) is a step of stirring the reaction solution. This is a process of reacting (3-aminepropyl) triethoxysilane with titanium dioxide under a nitrogen atmosphere.
상기 교반단계(S24)는, 상기 반응용액을 60℃ 내지 90℃의 온도하에서 15 내지 30시간동안 교반시키는 것이 바람직하며, 더욱 바람직하게는 70℃ 내지 80℃의 온도하에서 20 내지 25시간동안 교반시키는 것이 효과적이다. 70℃미만인 경우에는 온도가 낮아, 반응성이 저하됨으로써, 이산화티타늄에 아미노기가 충분히 결합되기 어려운 문제가 있으며, 90℃를 초과하는 경우에는 반응속도는 빨라지나, 그로 인해 이산화티타늄에 아미노기가 균일하게 결합되기 어려우며, 반응물질이 손상되는 문제가 있다. In the stirring step (S24), the reaction solution is preferably stirred for 15 to 30 hours at a temperature of 60 ℃ to 90 ℃, more preferably for 20 to 25 hours at a temperature of 70 ℃ to 80 ℃ Is effective. If the temperature is lower than 70 ° C., the temperature is low, and the reactivity decreases, thereby making it difficult to sufficiently bond the amino group to titanium dioxide. If the temperature exceeds 90 ° C., the reaction rate is increased, but the amino group is uniformly bound to the titanium dioxide. It is difficult to achieve, and there is a problem that the reactants are damaged.
또한, 필수적인 단계는 아니라, 교반단계(S24) 이후에, 건조단계(S25)를 추가하는 것이 바람직하다.In addition, after the stirring step (S24) is not an essential step, it is preferable to add a drying step (S25).
건조단계(S25)는 반응종료된 아미노기를 갖는 이산화티타늄을 톨루엔으로 세척하는 단계와 세척후에, 15 내지 30℃에서 24시간 내지 48시간동안 충분히 건조시키는 단계로 구분된다. 먼저, 세척을 통해, 미반응물질을 제거함으로써, 이후 입자에의 외첨반응성을 향상시키며, 건조과정을 통해, 이후의 입자표면처리공정을 용이하게 하는 역할을 한다. Drying step (S25) is divided into a step of washing the titanium dioxide having the reaction- terminated amino group with toluene and after washing, the step of sufficiently drying at 15 to 30 ℃ for 24 to 48 hours. First, by washing, by removing the unreacted material, thereby improving the external reactivity to the particles, and serves to facilitate the subsequent particle surface treatment process through the drying process.
다음으로, 본 발명에 의해 제조된 이산화티타늄 외첨제를 이용한 전자종이용 입자는, 도 2에 나타난 바와 같이, 베어입자(Bare particle, 10)와, 상기 베어입자(10)에 외첨된 외첨제입자(20), 그리고 외첨제입자(20)간의 화학적 결합(30) 및 외첨제입자(20)에 부여된 아미노기(40)를 포함하여 이루어진다. Next, the particles for electronic paper using the titanium dioxide external additive prepared according to the present invention, as shown in Figure 2, bare particles (Bare particle) 10, and the external additive particles attached to the bare particles (10) (20), and the chemical bond 30 between the external additive particles 20 and the amino group 40 attached to the external additive particles 20.
여기서, 베어입자(10)는 백색입자인 것이, 본 발명의 이산화티타늄을 이용한 전자종이용 입자 외첨제의 색상과 일치하여 바람직하다.Here, the bare particles 10 are preferably white particles in accordance with the color of the particle external additive for electronic paper using titanium dioxide of the present invention.
또한, 외첨제입자(20)의 전하는 (-)로, (+),(-)의 베어입자(10)에 모두 (-)전하를 띠는 본 발명의 외첨제입자(20)를 외첨함으로써, 입자간의 뭉침현상을 완전히 방지할 수 있다.In addition, the charge of the external additive particle 20 is negative (-), and by externally externalizing the external additive particle 20 of the present invention, which bears (-) charge to both the (+) and (-) bare particles 10, Aggregation between particles can be completely prevented.
이는 본 발명에 의해 제조된 외첨제입자(20)와 베어입자(10)와의 결합을 통해, 전자종이용 입자로서의 뭉침현상을 방지하고, 구동성 및 색채구현성이 우수하며, 최적의 전하를 띄고 있는 장점이 있다.This prevents agglomeration as particles for electronic paper through the combination of the external additive particle 20 and the bare particle 10 produced by the present invention, excellent driveability and color implementability, and exhibits an optimum charge. There is an advantage.
이상에서 본 발명의 바람직한 실시예를 설명하였으나, 본 발명은 다양한 변화와 변경 및 균등물을 사용할 수 있다. 본 발명은 상기 실시예를 적절히 변형하여 동일하게 응용할 수 있음이 명확하다. 따라서 상기 기재 내용은 하기 특허청구범위의 한계에 의해 정해지는 본 발명의 범위를 한정하는 것이 아니다.Although preferred embodiments of the present invention have been described above, the present invention may use various changes, modifications, and equivalents. It is clear that the present invention can be applied in the same manner by appropriately modifying the above embodiments. Accordingly, the above description does not limit the scope of the invention as defined by the limitations of the following claims.

Claims (17)

  1. 아미노기를 갖는 이산화티타늄을 첨가한 제 2용매에 베어입자를 첨가한 후, 분산시켜 반응준비용액을 제조하는 반응준비단계;및A reaction preparation step of preparing a reaction preparation solution by adding bare particles to a second solvent to which titanium dioxide having an amino group is added, and then dispersing; and
    상기 반응준비용액에 염산 및 글루타르알테하이드를 첨가하여 반응시키는 입자표면처리단계;를 포함하여 이루어지는 것을 특징으로 하는 이산화티타늄 외첨제를 이용한 전자종이용 입자의 표면처리방법Particle surface treatment step of reacting by adding hydrochloric acid and glutaraldehyde to the reaction preparation solution; Surface treatment method for particles for electronic paper using a titanium dioxide external additive, characterized in that comprises a
  2. 제 1항에 있어서, The method of claim 1,
    상기 반응준비단계에서, 상기 아미노기를 갖는 이산화티타늄은,In the reaction preparation step, the titanium dioxide having the amino group,
    이산화티타늄을 300 내지 500℃에서 15 내지 30시간동안 열처리하여 정제시키는 정제단계; 및A purification step of purifying titanium dioxide by heat treatment at 300 to 500 ° C. for 15 to 30 hours; And
    제 1용매에 상기 이산화티타늄을 첨가하여 반응시켜 아미노기를 갖는 이산화티타늄을 제조하는 아미노기치환단계;를 통해 제조되는 것을 특징으로 하는 이산화티타늄 외첨제를 이용한 전자종이용 입자의 표면처리방법The amino-substituted step of preparing the titanium dioxide having an amino group by the reaction by adding the titanium dioxide to the first solvent; Surface treatment method of the particle for electronic paper using a titanium dioxide external additive, characterized in that
  3. 제 1항 또는 제 2항에 있어서, The method according to claim 1 or 2,
    상기 반응준비단계에서, 상기 제 2용매는 이소프로필 알코올(Isopropyl Alcohol)인 것을 특징으로 하는 이산화티타늄 외첨제를 이용한 전자종이용 입자의 표면처리방법In the reaction preparation step, the second solvent is isopropyl alcohol (Isopropyl Alcohol) characterized in that the surface treatment method for particles for electronic paper using a titanium dioxide external additive.
  4. 제 1항 또는 제 2항에 있어서, The method according to claim 1 or 2,
    상기 반응준비단계에서, 상기 베어입자는, 모노머, 중합개시제 및 이온성모노머를 합성하여 제조되며, 상기 이온성 모노머는 스티렌설폰산(Styrene sulfonic acid) 또는 [2-(메타크릴옥시)에틸]트리메틸 암모늄 클로라이드 중 어느 하나인 것을 특징으로 하는 이산화티타늄 외첨제를 이용한 전자종이용 입자의 표면처리방법In the reaction preparation step, the bare particles are prepared by synthesizing a monomer, a polymerization initiator and an ionic monomer, and the ionic monomer is styrene sulfonic acid or [2- (methacryloxy) ethyl] trimethyl Surface treatment method of particles for electronic paper using titanium dioxide external additive, characterized in that any one of ammonium chloride
  5. 제 4항에 있어서, The method of claim 4, wherein
    상기 모노머는 메틸메타크릴레이트, 에틸렌테레프탈레이트, 스티렌술포네이트, 비닐아세트테이트, 메틸스티렌, 아크릴산, 부틸메타크릴레이트, 에틸메타크릴레이트, 2-에틸헥실아크릴레이트 또는 N-비닐카프로락탐 중 적어도 하나이며, 상기 중합개시제는 퍼옥시드화합물 또는 아조화합물 중 적어도 하나인 것을 특징으로 하는 이산화티타늄 외첨제를 이용한 전자종이용 입자의 표면처리방법The monomer is at least one of methyl methacrylate, ethylene terephthalate, styrenesulfonate, vinyl acetate, methyl styrene, acrylic acid, butyl methacrylate, ethyl methacrylate, 2-ethylhexyl acrylate or N-vinyl caprolactam Wherein the polymerization initiator is at least one of a peroxide compound or an azo compound, and the surface treatment method of the particle for electronic paper using the titanium dioxide external additive.
  6. 제 1항 또는 제 2항에 있어서, The method according to claim 1 or 2,
    상기 반응준비단계에서, 상기 제 2용매 100중량부에 대하여, 상기 아미노기를 갖는 이산화티타늄은 0.1 내지 1중량부를 첨가하는 것을 특징으로 하는 이산화티타늄 외첨제를 이용한 전자종이용 입자의 표면처리방법In the reaction preparation step, the titanium dioxide having the amino group with respect to 100 parts by weight of the second solvent, 0.1 to 1 part by weight of the surface treatment method for the electronic paper particles using titanium dioxide external additives
  7. 제 1항 또는 제 2항에 있어서, The method according to claim 1 or 2,
    상기 반응준비단계에서, 상기 제 2용매 100중량부에 대하여, 상기 베어입자는 1 내지 5중량부를 첨가하는 것을 특징으로 하는 이산화티타늄 외첨제를 이용한 전자종이용 입자의 표면처리방법In the reaction preparation step, with respect to 100 parts by weight of the second solvent, the bare particles surface treatment method of the electronic paper particles using titanium dioxide external additive, characterized in that 1 to 5 parts by weight is added.
  8. 제 1항 또는 제 2항에 있어서, The method according to claim 1 or 2,
    상기 입자표면처리단계에서, 상기 제 2용매 100중량부에 대하여, 상기 염산 및 글루타르알테하이드는 각각 60 내지 90중량부를 첨가하는 것을 특징으로 하는 이산화티타늄 외첨제를 이용한 전자종이용 입자의 표면처리방법In the particle surface treatment step, the hydrochloric acid and glutaraldehyde are added to 60 parts by weight to 90 parts by weight with respect to 100 parts by weight of the second solvent, and the surface treatment of the particles for electronic paper using the titanium dioxide external additive. Way
  9. 제 1항 또는 제 2항에 있어서, The method according to claim 1 or 2,
    상기 입자표면처리단계는, 상기 반응준비용액을 10 내지 30℃에서 마그네틱바를 사용하여 교반하면서, 상기 염산 및 글루타르알테하이드를 첨가하는 것을 특징으로 하는 이산화티타늄 외첨제를 이용한 전자종이용 입자의 표면처리방법The particle surface treatment step, the surface of the particles for electronic paper using titanium dioxide external additive, characterized in that the hydrochloric acid and glutaraldehyde is added while stirring the reaction preparation solution using a magnetic bar at 10 to 30 ℃ Treatment method
  10. 제 1항 또는 제 2항에 있어서, The method according to claim 1 or 2,
    상기 입자표면처리단계에서, 반응시간은 1 내지 3시간인 것을 특징으로 하는 이산화티타늄 외첨제를 이용한 전자종이용 입자의 표면처리방법In the particle surface treatment step, the reaction time is 1 to 3 hours, the surface treatment method of the particles for electronic paper using a titanium dioxide external additive, characterized in that
  11. 제 2항에 있어서, The method of claim 2,
    상기 아미노기치환단계에서, 상기 제 1용매는 톨루엔인 것을 특징으로 하는 이산화티타늄 외첨제를 이용한 전자종이용 입자의 표면처리방법In the amino group substitution step, the first solvent is toluene surface treatment method of the particle for electronic paper using a titanium dioxide external additive, characterized in that
  12. 제 2항 또는 제 11항에 있어서, The method according to claim 2 or 11, wherein
    상기 아미노기치환단계는, 상기 제 1용매에 상기 이산화티타늄을 첨가한 후, 분산시켜 반응용액을 제조하는 반응용액 제조단계;The amino group substitution step, the reaction solution manufacturing step of preparing a reaction solution by adding the titanium dioxide to the first solvent, and then dispersing;
    상기 반응용액을 질소분위기하에서 가열하는 가열단계; A heating step of heating the reaction solution under a nitrogen atmosphere;
    상기 반응용액에 (3-아민프로필)트리에톡시실란((3-aminopropyl) triethoxysilane)을 첨가하는 에톡시실란 첨가단계; 및An ethoxysilane addition step of adding (3-aminopropyl) triethoxysilane to the reaction solution; And
    상기 반응용액을 교반시키는 교반단계;를 포함하여 이루어지는 것을 특징으로 하는 이산화티타늄 외첨제를 이용한 전자종이용 입자의 표면처리방법Stirring step of stirring the reaction solution; Surface treatment method of particles for electronic paper using a titanium dioxide external additive, characterized in that comprises a
  13. 제 12항에 있어서, The method of claim 12,
    상기 반응용액 제조단계에서, 상기 제 1용매 100중량부에 대하여, 상기 이산화티타늄은 20 내지 50중량부인 것을 특징으로 하는 이산화티타늄 외첨제를 이용한 전자종이용 입자의 표면처리방법In the reaction solution preparation step, the titanium dioxide is a surface treatment method of the particle for electronic paper using titanium dioxide external additive, characterized in that 20 to 50 parts by weight based on 100 parts by weight of the first solvent.
  14. 제 12항에 있어서, The method of claim 12,
    상기 가열단계는, 상기 반응용액의 온도를 60℃ 내지 90℃의 온도로 유지시키는 것을 특징으로 하는 이산화티타늄 외첨제를 이용한 전자종이용 입자의 표면처리방법The heating step, the surface treatment method of the particle for electronic paper using a titanium dioxide external additive, characterized in that to maintain the temperature of the reaction solution at a temperature of 60 ℃ to 90 ℃.
  15. 제 12항에 있어서, The method of claim 12,
    상기 에톡시실란첨가단계에서, 상기 제 1용매 100중량부에 대하여, 상기 (3-아민프로필)트리에톡시실란은 20 내지 50중량부인 것을 특징으로 하는 이산화티타늄 외첨제를 이용한 전자종이용 입자의 표면처리방법In the ethoxysilane addition step, with respect to 100 parts by weight of the first solvent, the (3-aminepropyl) triethoxysilane is 20 to 50 parts by weight of the electronic paper particles using the titanium dioxide external additive, characterized in that Surface treatment method
  16. 제 12항에 있어서, The method of claim 12,
    상기 교반단계는, 상기 반응용액을 60℃ 내지 90℃의 온도하에서 15 내지 30시간동안 교반시키는 것을 특징으로 하는 이산화티타늄 외첨제를 이용한 전자종이용 입자의 표면처리방법The stirring step, the surface treatment method of the particles for electronic paper using a titanium dioxide external additive, characterized in that the reaction solution is stirred for 15 to 30 hours at a temperature of 60 ℃ to 90 ℃.
  17. 제 1항 내지 제 16항 중 어느 한 항에 의해 제조된 것을 특징으로 하는 이산화티타늄 외첨제를 이용한 전자종이용 입자Electron paper particles using a titanium dioxide external additive, characterized in that prepared by any one of claims 1 to 16
PCT/KR2012/002818 2011-04-14 2012-04-13 Method for surface-treating electronic paper particle using titanium dioxide additive and electronic paper particle using titanium dioxide additive manufactured thereby WO2012141528A2 (en)

Applications Claiming Priority (2)

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KR10-2011-0034888 2011-04-14
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