WO2010126218A1 - Composition de particules fluidiques et méthode d'élaboration de particules fluidiques l'utilisant - Google Patents

Composition de particules fluidiques et méthode d'élaboration de particules fluidiques l'utilisant Download PDF

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WO2010126218A1
WO2010126218A1 PCT/KR2009/007438 KR2009007438W WO2010126218A1 WO 2010126218 A1 WO2010126218 A1 WO 2010126218A1 KR 2009007438 W KR2009007438 W KR 2009007438W WO 2010126218 A1 WO2010126218 A1 WO 2010126218A1
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parts
weight
particles
solvent
flowable
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PCT/KR2009/007438
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English (en)
Korean (ko)
Inventor
최경호
이상국
임은희
안유선
김성욱
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한국생산기술연구원
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Priority claimed from KR1020090036764A external-priority patent/KR101098538B1/ko
Priority claimed from KR1020090036766A external-priority patent/KR101015615B1/ko
Priority claimed from KR1020090036761A external-priority patent/KR101039127B1/ko
Priority claimed from KR1020090036765A external-priority patent/KR101015614B1/ko
Priority claimed from KR1020090036763A external-priority patent/KR101098536B1/ko
Application filed by 한국생산기술연구원 filed Critical 한국생산기술연구원
Publication of WO2010126218A1 publication Critical patent/WO2010126218A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • 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 flowable particle composition and a method for producing flowable particles using the same, and more particularly, to a flowable particle comprising silica (SiO 2 ), tetraethyl orthosilicate, tetranomal butyl titanate, etc., in a polymer.
  • silica SiO 2
  • tetraethyl orthosilicate tetranomal butyl titanate, etc.
  • the flowable particle composition and the flowable particle using the same to improve the reflectance, to control the aggregation phenomenon between the charged particles, to provide a flow particle having a low initial drive voltage, excellent durability and flowability It relates to a manufacturing method of.
  • Electronic paper image display device technology generally used includes an electrophoretic method of microencapsulating a dispersion consisting of dispersed particles and a colored solution and disposing it 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.
  • the collision charging type electronic paper image display apparatus includes charged particles 60 and 70 charged according to the applied electrode polarity when sufficient voltage is applied to the upper electrode 30 and the lower electrode 40. It is attracted to each electrode. For example, when ⁇ voltage is applied to the lower electrode 40 and + voltage is applied to the upper electrode 30, the black charged particles 60 positively charged by the coulomb force move toward the lower substrate 20. In addition, the negatively charged white charged particles 70 move toward the upper substrate 10. As a result, since the white charged particles 70 are located on the upper substrate 10 side, the white charged particles 70 appear white when viewed from the outside. On the contrary, when + voltage is applied to the lower electrode 40 and ⁇ voltage is applied to the upper electrode 30, the black charged particles 60 move toward the upper substrate 10, and thus appear black.
  • a technique for forming a charged particle having a fluidity (hereinafter, referred to as a 'fluid particle') should be accompanied, and the fluid particle is generally illustrated in FIG. 2.
  • dye / dye 3 is shown.
  • the flowable particles include an external blending method using a mixer by adding an external additive 4 to a dispersion solvent including a polymer particle, a charge control agent, and a dye / dye (3). have.
  • the polymer particles 1 and the external additives 4 are physically bonded, and due to the limitation of the durability of the physical bonding, the external components easily fall off.
  • the external additive 4 easily falls in this way, the charged particles cannot sufficiently respond to the same applied voltage, and since the charging characteristics also change easily, there arises a problem of deterioration in image quality.
  • 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.
  • the present invention is to solve the above problems, an object of the present invention, by using tetraethyl orthosilicate (tetraethyl orthosilicate) and tetraolmalbutyl titanate and silica (SiO 2 ), excellent bonding durability, fluidity and It is to provide a flowable particle composition which is excellent in reflectance and has little occurrence of aggregation between particles. In addition, it is to provide a flowable particle composition that can easily control the particle distribution by adjusting to the optimum pH.
  • Another object of the present invention is to chemically bond titanium dioxide (TiO 2 ) and silica (SiO 2 ) to a monomer by one dispersion polymerization without the use of separate polymer particles, thereby eliminating the need for a separate process.
  • Phosphorus effect is excellent, silane surface treatment to solve the agglomeration phenomenon between the charged particles, and to provide a method for producing fluid particles with a lower initial drive voltage.
  • the flowable particle composition according to the present invention for achieving the above object, based on the solvent and 100 parts by weight of the solvent, 5 to 20 parts by weight of monomer, 0.1 to 3 parts by weight of polymerization initiator, tetranomal butyl titanium It is characterized in that it comprises 0.5 to 2 parts by weight of silicate, 0.7 to 3 parts by weight of silica.
  • the second embodiment is based on the solvent and 100 parts by weight of the solvent, 5 to 20 parts by weight of monomer, 0.1 to 3 parts by weight of polymerization initiator, 0.5 to 2 parts by weight of tetraolmalbutyl titanate, and 0.7 to tetraethyl orthosilicate. Characterized in that it comprises 5 parts by weight.
  • the dispersion stabilizer further comprises 0.5 to 15 parts by weight, the dispersion stabilizer is characterized in that the poly vinyl pyrrolidone (Poly Vinyl pyrrolidone).
  • the monomer is styrene, methyl methacrylate, ethylene terephthalate, styrene sulfonate, vinyl acetate, methyl styrene, acrylic acid, butyl methacrylate, ethyl methacrylate, 2-ethylhexyl acrylate, N-vinyl caprolactam It is characterized in that at least one of.
  • the polymerization initiator is characterized in that the 2,2'-azobis (isobutyramidine) hydrochloride (2,2'-azobis (isobutyramidine) hydrochloride), the solvent is at least one of water or ethanol
  • the flowable particle composition is characterized in that the hydrogen ion index (pH) is 8 to 13.
  • the method for producing the flowable particles according to the present invention provides a core by mixing 5 to 20 parts by weight of a monomer and 0.1 to 3 parts by weight of a polymerization initiator with respect to 100 parts by weight of a solvent and a solvent.
  • Forming a core forming step A dissolution step of dissolving tetranomal butyl titanate in ethanol (EtOH); A first mixing step of preparing a first mixed solution by mixing silica in the core with 0.7 to 3 parts by weight based on 100 parts by weight of the solvent; A second mixing step of preparing a second mixed solution by mixing 0.5 to 2 parts by weight of tetranomal butyl titanate with respect to 100 parts by weight of the solvent to the first mixed solution; the second mixed solution at a temperature of 40 to 90 ° C.
  • the second embodiment is a core forming step of forming a core by mixing a solvent and 100 parts by weight of a solvent, 5 to 20 parts by weight of monomer, 0.1 to 3 parts by weight of polymerization initiator, 0.5 to 15 parts by weight of dispersion stabilizer; A dissolution step of dissolving tetranomal butyl titanate in ethanol (EtOH); A first mixing step of preparing a first mixed solution by mixing tetraethyl orthosilicate in the core in an amount of 0.7 to 5 parts by weight based on 100 parts by weight of the solvent; A second mixing step of preparing a second mixed solution by mixing tetraolmalbutyl titanate with 0.5 to 2 parts by weight with respect to 100 parts by weight of the solvent to the first mixed solution; A polymerization step of polymerizing the second mixed solution at a temperature of 40 to 90 ° C. for 30 to 50 hours to produce fluid particles; It characterized in that it comprises a; drying step of drying the flowable particles.
  • the dispersion stabilizer further comprises 0.5 to 15 parts by weight, the dispersion stabilizer is characterized in that the poly vinyl pyrrolidone (Poly Vinyl pyrrolidone).
  • the surface treatment step of treating the surface of the flowable particles with silane Selecting particles to select the particles using a sieve made of a hole of 10 to 30 ⁇ m;
  • the monomer is styrene, methyl methacrylate, ethylene terephthalate, styrene sulfonate, vinyl acetate, methyl styrene, acrylic acid, butyl methacrylate, ethyl methacrylate, 2-ethylhexyl acrylate, N
  • the polymerization initiator is 2,2'-azobis (isobutyramidine) hydrochloride (2,2'-azobis (isobutyramidine) hydrochloride) It is characterized by that.
  • the solvent is at least one of water and ethanol
  • the silane in the surface treatment step, is tridecafluoro-1,1,2,2-tetrahydrooctyltrie Tridecafluoro-1,1,2,2-tetrahydro octyltriethoxysilane or 3,3,3-trifluoropropyltrimethoxysilane or ethoxytrimethylsilane It is characterized by at least one of.
  • the silane in the surface treatment step, is characterized in that it comprises 5 to 10 parts by weight based on 100 parts by weight of the solvent.
  • the bonding is excellent in durability, fluidity and reflectance, intergranular aggregation There is an advantage to control the occurrence.
  • FIG. 1 is a cross-sectional view showing a cell structure of a collision charging type electronic paper image display apparatus according to the prior art
  • Figure 2 is a cross-sectional view showing the particles used in the electronic paper image display device according to the prior art
  • Figure 3 is a TEM photograph of the particles produced according to the PVP addition and pH control
  • FIG. 4 is a graph showing the particle size distribution according to FIG.
  • FIG. 5 is a graph analyzing the particles according to FIG. 3 according to an infrared spectroscopy method
  • FIG. 6 is a graph measuring the inorganic content according to the temperature of the particles according to FIG.
  • FIG. 9 is a TEM photograph of particles (with PVP) according to the content ratio of tetraolmalbutyl titanate and tetraethylorthosilicate.
  • FIG. 10 is a graph showing the conversion rate of tetraolmalbutyl titanate according to the content ratio of tetraethylorthosilicate and tetraolmalbutyl titanate
  • 11 is a graph showing the size distribution of particles according to the content ratio of tetraethylorthosilicate and tetraolmalbutyl titanate
  • V 12 is a graph showing the driving voltage (V) according to the content ratio of tetraethylorthosilicate and tetraolmalbutyl titanate
  • FIG. 13 is a flow chart sequentially showing a method for producing flowable particles according to the present invention
  • FIG. 14 is a TEM photograph of particles produced according to a mixing sequence of tetraethylorthosilicate and tetraolmalbutyl titanate.
  • FIG. 15 is a graph showing particle size distribution according to FIG. 14.
  • V 16 is a graph showing the driving voltage (V) of the particles according to the silane treatment
  • V 17 is a graph showing the driving voltage (V) of the particles according to the silane treatment
  • V driving voltage
  • V driving voltage
  • pH hydrogen ion index
  • V driving voltage
  • Polymerization of the polymer is mainly performed by emulsion polymerization using a surfactant such as sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB), dispersion polymerization and suspension polymerization.
  • a surfactant such as sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB)
  • SDS sodium dodecyl sulfate
  • CTAB cetyltrimethylammonium bromide
  • the inventors of the present invention have prepared a fluid particle by performing emulsion polymerization (soap-free emulsion polymerization) or dispersion polymerization excluding a surfactant to polymerize polymer particles. It is proposed a manufacturing method that can increase the yield by reducing the number of working processes and economical, which can obtain the flowable particles in only a step.
  • the surfactant does not enter during the polymerization process, but includes a polymerization initiator, a dispersion stabilizer or a functional group exhibiting ionic properties to the polymer chain to be polymerized, and thus the interface by the interaction thereof A colloidal stabilizing effect similar to that of the active agent was obtained.
  • the silica particles and the titanium dioxide particles adhered well to the surface of the polymer particles, and were able to form flowable particles having a small particle size distribution.
  • the flowable particle composition according to the present invention comprises a solvent, a monomer, a polymerization initiator, tetranomal butyl titanate (Ti (Obu) 4 ), and silica.
  • the second embodiment includes a solvent, a monomer, a polymerization initiator, tetranomal butyl titanate (Ti (Obu) 4 ), and tetraethyl orthosilicate.
  • the solvent may be used alone or mixed with water or ethanol, and the monomer is not particularly limited as long as it is capable of non-emulsifying polymerization, methyl methacrylate, ethylene terephthalate, styrene sulfonate, vinyl acetate, methyl styrene , Monomers such as acrylic acid, butyl methacrylate, ethyl methacrylate, 2-ethylhexyl acrylate, N-vinyl caprolactam, or the like can be used alone or in a copolymerized manner, and preferably styrene is most effective. to be.
  • the content of the monomer is preferably 5 to 20 parts by weight, more preferably 8 to 15 parts by weight with respect to 100 parts by weight of the solvent.
  • the monomer is added in less than 5 parts by weight, there is a problem that the resulting polymer particles are less likely to be charged, and when it exceeds 20 parts by weight, silica and titanium dioxide (TiO 2 ) as external additives sufficiently cover the surface of the polymer particles. There is a problem that the durability and fluidity is deteriorated due to not wrapped.
  • silica and titanium dioxide (TiO 2 ) are chemically bonded to the surface of the polymer particles produced through the polymerization of the monomer. This is accomplished by the mechanism whereby the synthesis initiator is a cation, and the negative charges of silica and titanium dioxide (TiO 2 ) are bonded to form strong ionic bonds.
  • Polymerization initiators used herein include all free radical polymerization initiators capable of triggering non-emulsification polymerization generally used.
  • the polymerization initiator may in principle comprise both peroxides and azo compounds, said peroxides being in principle inorganic peroxides such as hydrogen peroxide or peroxodisulfate such as mono- or di-alkali metals of peroxodisulfate Salts or ammonium salts, examples of which are mono- and di-sodium and -potassium salts, or ammonium salts, or may be organic peroxides such as alkyl hydroperoxides, for example tert-butyl, p- Menthyl and cumyl hydroperoxide, and also dialkyl or diaryl peroxides, such as di-tert-butyl peroxide or dicumyl peroxide.
  • the compounds used are mainly 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (amidinopropyl) Dihydrochloride).
  • 2,2'-azobis (isobutyramidine) hydrochloride (2,2'-azobis (isobutyramidine) hydrochloride) (hereinafter referred to as 'AIBA') is most efficiently used as a polymerization initiator.
  • AIBA has the following structure.
  • a bond is formed due to the interaction between the cation initiator AIBA and silica and titanium dioxide (TiO 2 ), which is a basic charge because the silica particles have a negative charge at a hydrogen ion index (pH) of 3 or higher.
  • TiO 2 titanium dioxide
  • the polymerization initiator preferably contains 0.1 to 3 parts by weight, more preferably 1 to 2 parts by weight based on 100 parts by weight of the solvent. If the polymerization initiator is less than 0.1 part by weight, the interaction between silica and titanium dioxide (TiO 2 ) is difficult, and no bond is formed. When the polymerization initiator is more than 3 parts by weight, the cation is excessive, so that the bonding strength is weak and economical inferior. there is a problem.
  • the present invention includes a dispersion stabilizer in order to achieve a dispersion polymerization reaction when the particles are formed by dispersion polymerization.
  • a dispersion stabilizer various materials can be used, but it is effective to use poly vinyl pyrrolidone (hereinafter, referred to as 'PVP') most preferably after several experiments. PVP increases the dispersion stability of the particles.
  • the dispersion stabilizer preferably contains 0.5 to 15 parts by weight, and more preferably 5 to 8 parts by weight based on 100 parts by weight of the solvent.
  • the dispersion stabilizer is less than 0.5 parts by weight, the dispersion of the monomer is not good, the dispersion polymerization reaction is not performed smoothly, there is a problem that the size of the flowable particles are uneven, the possibility of aggregation between particles increases.
  • Figure 4 is an experimental result of how the PVP and pH affect the particle size and evenness
  • Figure 4a is a core particle in the presence of PVP
  • Figure 4b is a core particle in the absence of PVP
  • Figure 4c is Flowable Particles with PVP
  • FIG. 4D is a flowable particle with PVP and pH
  • FIG. 4E is a graph of the size and level of flowable particles with no PVP and pH 10.
  • FIG. 4 As shown in FIG. 4, when PVP is present, the particles appear to be evenly uniform, and when the pH is maintained at 10, the size of the particles is also small and even. Therefore, in the case of FIG. 4D where PVP is present and the pH is maintained at 10, it is proved by the experimental results that the performance shows the best flowable particles, so that the performance of the best flowable particles is ensured in the case of the scope of the present invention. Able to know.
  • Figure 5 is a graph showing the results of the experiment according to the presence or absence of PVP and pH control by infrared spectroscopy (hereinafter referred to as IR).
  • IR infrared spectroscopy
  • FIG. 6 is a graph measuring the inorganic content according to the presence or absence of PVP under the same conditions as (b) and (c) of FIG. 5, and (b) also falling within the scope of the present invention showed the highest inorganic content. The results show that the most bond is formed.
  • the flowable particle composition of the present invention includes tetraolmalbutyl titanate (Ti (Obu) 4 ), which is converted into the form of titanium dioxide (TiO 2 ) in the process of mixing with the monomer, thereby binding to the monomer, the flowable particle It is effective to greatly increase the reflectance of. This reflectivity increase effect can be seen through the reflectance comparison test results in Table 1 below.
  • silica is included to bond with the monomer as an external additive of the flowable particles.
  • the silica particles are not particularly limited as long as they can form a stabilization layer, but may include LUDOX AM30®, SS-SOL 30F®, Aerosil®, and the like, most preferably LUDOX SM30®.
  • the hydrogen ion index (pH) is preferably maintained at 8 to 13, and most preferably at 10 to 11 is effective.
  • the hydrogen ion index (pH) is less than 8 or more than 13, the coupling reaction between the monomer and silica and titanium dioxide (TiO 2 ) does not occur well, and thus there is a problem in that stable fluid particles cannot be prepared.
  • the tetranomal butyl titanate (Ti (Obu) 4 ) preferably contains 0.5 to 2 parts by weight based on 100 parts by weight of the solvent, and the silica includes 0.7 to 3 parts by weight based on 100 parts by weight of the solvent. It is desirable to.
  • Tetraolmalbutyl titanate is converted to titanium dioxide (TiO 2 )
  • tetraethylorthosilicate (TEOS) is converted to silica (SiO 2 ) to the monomer
  • Figure 10 and Table 2 is tetraolmalbutyl titanate and tetra
  • TEOS tetraethylorthosilicate
  • FIG. 11A is a core particle before tetraethylorthosilicate and tetranomalbutyl titanate are mixed
  • FIG. 11B is a case in which the content ratio of TEOS / Ti (Obu) 4 is 10.
  • FIG. 11C is a diagram of TEOS / Ti (Obu) 4 .
  • FIG. 11D is a case where the content ratio of TEOS / Ti (Obu) 4 is 1.5
  • FIG. 11E is a case in which the content ratio of TEOS / Ti (Obu) 4 is 0.5.
  • FIGS. 11A and 11B belonging to the TEOS / Ti (Obu) 4 content range of the present invention showed that the size of the particles was small and even, indicating that the particles were well bonded.
  • the initial driving voltage of (v) according to the content ratio of tetraethylorthosilicate and tetranomal butyl titanate when TEOS / Ti (Obu) 4 content ratio is 4 (a), TEOS / Ti Comparing (b) in the case of (Obu) 4 content ratio of 1.5, the initial operating voltage of (a) in the TEOS / Ti (Obu) 4 content range of the present invention is 120v, which is much lower than 160v of (b). It can be seen that it represents the driving voltage.
  • the tetraolmalbutyl titanate (Ti (Obu) 4 ) preferably contains 0.5 to 2 parts by weight based on 100 parts by weight of the solvent, and the tetraethylorthosilicate is 0.7 to 5 parts by weight of 100 parts by weight of the solvent. It is preferred to include parts by weight.
  • the flowable particle composition according to the present invention may include a charge control agent such as a positive (+) charge control agent or a negative (-) charge control agent, if necessary, and an organic colorant. Or inorganic colorants may be additionally included.
  • the charge control agent may be a positively charged charge control agent such as a nigrosine dye, a triphenylmethane compound, a quaternary ammonium salt compound, a polyamine resin or an imidazole derivative, a salicylic acid metal complex, or a metal (metal ion or metal).
  • Negative charge charge control agents such as azo dyes, oil-soluble dyes containing metals, quaternary ammonium salt compounds, calix arene compounds, boron-containing compounds (boron benzyl complex) or nitroimidazole derivatives;
  • any charge control agent usable for the flowable particles for the electronic paper image display device may be included.
  • the colorant may be an organic colorant such as nigrosine, methylene blue, quinoline yellow, or rose bengal, titanium oxide, zinc oxide, zinc sulfide, antimony oxide, calcium carbonate, light white, talc, silica or calcium silicate.
  • the method for producing the flowable particles is the same as the description of the flowable particle composition, and will be described below mainly on the characteristics of the production method.
  • the manufacturing method of the flowable particles according to the present invention core forming step (S10), dissolution step (S20), the first mixing step (S30), the second mixing step (S40), the polymerization step ( S50), drying step (S60), surface treatment step (S70), the particle selection step (S80), pH adjustment step (S31, S41) is made to include.
  • the core forming step (S10) is a step of forming a core by mixing 5 to 20 parts by weight of monomer and 0.1 to 3 parts by weight of a polymerization initiator with respect to 100 parts by weight of a solvent and a solvent. In the case of dispersion polymerization, 0.5 to 15 parts by weight of the dispersion stabilizer is further mixed.
  • the core particles are formed by mixing about 15 to 24 hours, including the type and content of monomers and polymerization initiators as discussed in the fluid particle composition.
  • Dissolution step (S20) is a step of dissolving tetranol butyl titanate in ethanol (EtOH). This is a step for controlling the reaction rate of tetranomal butyl titanate and silica, and after dissolving tetranomal butyl titanate in ethanol proceeds to the following mixing process.
  • first mixing step (S30) 0.7 to 3 parts by weight of silica is mixed with 100 parts by weight of the solvent to prepare a first mixture solution, or tetraethyl orthosilicate is added to the core with 100 parts of the solvent. 0.7 to 5 parts by weight of the mixture is added to prepare a first mixed solution.
  • the second mixing step (S40) is a step of preparing a second mixture solution by mixing 0.5 to 2 parts by weight of tetranomal butyl titanate with respect to 100 parts by weight of the solvent in the first mixture solution.
  • Tetranomal butyl titanate has an effect of significantly improving the reflectance of the flowable particles.
  • Figure 15a is a graph of the size of the core particles passed through the core forming step (S10)
  • Figure 15b is a particle size graph for Figure 8 (a)
  • Figure 15c is a particle size graph for Figure 14 (b)
  • (b) of the present invention even more (a) the size of the particles, silica and titanium dioxide is combined without forming a particle.
  • the acidic or alkaline solution is added to the first mixed solution or the second mixed solution in the first mixing step or the second mixing step to obtain a hydrogen ion index (pH) from 8 to 8.
  • Step 13 is adjusted.
  • an acid such as hydrochloric acid and sulfuric acid or an alkaline solution such as ammonia or sodium hydroxide is added to make a basic environment as necessary. It is desirable to make a phosphorus environment. Most preferably it is effective that the pH is 10-11.
  • the hydrogen ion index (pH) is less than 8 or more than 13
  • the coupling reaction between the monomer, silica, and titanium dioxide (TiO 2 ) does not occur well, and there is a problem in that stable fluid particles cannot be prepared.
  • silica particles are basic, a separate acid or base may not be required.
  • the polymerization step (S50) is a step of polymerizing the second mixed solution at a temperature of 40 to 90 ° C. for 30 to 50 hours to prepare flowable particles.
  • the polymerization temperature is preferably maintained at a temperature of 40 to 90 ° C, more preferably 60 to 75 ° C.
  • the polymerization step (S50) is to perform the polymerization while stirring, supplying an inert gas such as nitrogen (N 2 ) or argon (Ar), while removing the dissolved oxygen contained in the solvent, preferably 15 to 24 hours More preferably, the polymerization by the non-emulsification polymerization method is performed for 18 to 22 hours. If the polymerization time is less than 15 hours or more than 24 hours, the polymerization reaction is not smoothly performed, there is a problem that a stable fluid particles can not be produced.
  • Drying step (S60) is a step of drying the flowable particles. This may be carried out in accordance with the drying step of the conventional method for producing a fluid particle, preferably dry using a supercritical process or atmospheric pressure drying of the wet gel subjected to surface hydrophobization and solvent substitution (for example, normal oven drying), etc. Can be used. In addition, lyophilization can be performed. This may be used after cooling the mixed aqueous solution containing the polymerized polymer to -100 ° C to -10 ° C to solidify the material, and then lowering the pressure to 4.6torr or less to sublimate the water contained in the freeze powder. .
  • S70 is a step of treating the surface of the flowable particles with silane. This is a process of hydrophobizing the surface of the flowable particles in order to prevent agglomeration between particles due to the presence of OH groups at the ends of the prepared flowable particles.
  • the OH group of the fluid particles is removed by causing hydrolysis and condensation reaction using salane.
  • the silane may be any kind of silane compound, but tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane, CF 3- TES) or 3,3,3-trifluoropropyltrimethoxysilane (3,3,3-trifluoropropryl methoxysilane, CF 3 -TMS) or ethoxytrimethylsilane
  • ETMS ethoxytrimethylsilane
  • the silane preferably contains 5 to 10 parts by weight, and most preferably 6.5 to 8 parts by weight based on 100 parts by weight of the solvent. If it is less than 5 parts by weight, the effect of preventing aggregation between the fluid particles is insignificant, and if it exceeds 10 parts by weight, there is a problem that the initial driving voltage of the fluid particles is increased.
  • the hydrogen ion index (pH) in the surface treatment step (S70) is preferably maintained at 8 to 13, most preferably at 10 to 11 is effective. If the hydrogen ion index (pH) is less than 8 or exceeds 13, there is a problem that the initial drive voltage increases.
  • the particle selection step (S80) is a step of selecting only particles of an appropriate size by passing the manufactured fluid particles through a sieve in which a plurality of holes exist. It is preferable that the hole size of the sieve in the particle selection step (S80) is 10 to 30 ⁇ m, most preferably 15 to 25 ⁇ m. If the size of the hole is less than 10 ⁇ m, there is a problem that most of the particles are filtered smaller than the size of the particles, if the size exceeds 30 ⁇ m most of the particles are not filtered, there is a problem that the effect of particle selection.
  • the initial driving voltage (v) was compared when the sieve was not sifted, when the sieve was hit with a 25 ⁇ m sieve, and when the sieve was hit with a 15 ⁇ m sieve.
  • the initial driving voltage was measured to be low, and the sieve stage showed excellent flowable particle performance.
  • the present invention is to improve the reflectance by the non-emulsification polymerization or dispersion polymerization by producing a flowable particles in which a polymer (silica (SiO 2 ), tetraethyl orthosilicate, tetraol maltbutyl titanate, etc.) to the polymer by emulsion-free polymerization or dispersion polymerization,
  • a polymer silicon (SiO 2 ), tetraethyl orthosilicate, tetraol maltbutyl titanate, etc.
  • the present invention relates to a fluid particle composition for controlling agglomeration phenomenon, to provide a fluid particle having a low initial driving voltage, and excellent in durability and fluidity, and a method for producing the fluid particle using the same, and industrial applicability is recognized.

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  • Polymers & Plastics (AREA)
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Abstract

L'invention porte sur une composition de particules fluidiques et sur une méthode d'élaboration de particules fluidiques l'utilisant. Ladite composition comprend: des solvants; de 5 à 20 parties en poids d'un monomères; de 0,1-3 parties en poids d'un initiateur de polymérisation ; de 0,5-2 parties en poids de titanate de tétra n-butyle; et de 0.7-3 parties en poids de silice, basées sur 100 parties en poids de solvant. Ladite composition,qui peut réguler l'agrégation de particules chargées et de particules fluidiques, présente une excellente durabilité et une excellente fluidité, obtenues par une synthèse appropriée d'un initiateur de synthèse, d'un nanocomposite de synthèse, etc. La méthode d'élaboration des particules fluidiques de l'invention permet une fixation uniforme des particules de silice sur la surface des particules de polymère et peut facilement réguler la distribution des particules en portant le pH à un niveau optimum. L'invention permet en outre d'abaisser la tension initiale d'activation des particules fluidiques.
PCT/KR2009/007438 2009-04-27 2009-12-11 Composition de particules fluidiques et méthode d'élaboration de particules fluidiques l'utilisant WO2010126218A1 (fr)

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
KR10-2009-0036765 2009-04-27
KR10-2009-0036764 2009-04-27
KR1020090036764A KR101098538B1 (ko) 2009-04-27 2009-04-27 Ｔｅｏｓ를 이용한 유동성 입자조성물 및 이를 이용한 유동성 입자의 제조방법
KR1020090036766A KR101015615B1 (ko) 2009-04-27 2009-04-27 테트라놀말부틸티타네이트 유동성 입자를 이용한 전자종이 디스플레이장치 및 그 제조방법
KR10-2009-0036761 2009-04-27
KR1020090036761A KR101039127B1 (ko) 2009-04-27 2009-04-27 유동성 입자 조성물 및 이를 이용한 유동성 입자의 제조방법
KR1020090036765A KR101015614B1 (ko) 2009-04-27 2009-04-27 Ｔｅｏｓ 유동성 입자를 이용한 전자종이디스플레이 장치 및 그 제조방법
KR1020090036763A KR101098536B1 (ko) 2009-04-27 2009-04-27 테트라놀말부틸티타네이트를 이용한 유동성 입자의 제조방법
KR10-2009-0036763 2009-04-27
KR10-2009-0036766 2009-04-27

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WO2010126218A1 true WO2010126218A1 (fr) 2010-11-04

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060024437A1 (en) * 1997-08-28 2006-02-02 E Ink Corporation Electrophoretic particles, and processes for the production thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060024437A1 (en) * 1997-08-28 2006-02-02 E Ink Corporation Electrophoretic particles, and processes for the production thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DING, XUEFENG ET AL.: "Silicon dioxide as coating on polystyrene nanoparticles in situ emulsion polymerization", MATERIALS LETTERS, vol. 58, no. ISS.11, April 2004 (2004-04-01), pages 1722 - 1725, XP004495336, DOI: doi:10.1016/j.matlet.2003.11.017 *
FU, XIAO-AN ET AL.: "Synthesis of titania-coated silica nanoparticles using ono-ionic water- in-oil", COLLOIDS AND SURFACES A: PHYSICOCHEMICAL AND ENGINEERING ASPECTS, vol. 178, no. ISSUES, 15 March 2001 (2001-03-15), pages 151 - 156 *
HWANG, SEONG-TAE ET AL.: "Preparation and characterization of poly(MSMA-co-MMA)- Ti02/Si02 nanocomposites using the colloidal Ti02/Si02 particles via blending method", COLLOIDS AND SURFACES A: PHYSICOCHEMICAL AND ENGINEERING ASPECTS, vol. 259, 31 May 2005 (2005-05-31), pages 63 - 69 *

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