JP2012068392A - Particle for display medium and information display device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a complex particle for a display medium used for an information display device, which is capable of improving electric charge retention capability and also adjusting a triboelectric charge amount.SOLUTION: A particle for a display medium constituting a display medium used in an information display device is formed as a complex particle where child particles are adhered to the surface of a mother particle. The child particle is comprised of a core part and a shell part covering it. The core part is comprised of a condensation product of a first amino compound essentially including melamine with formaldehyde. The shell part includes a first shell layer comprised of a condensation product of a second amino compound essentially including guanamine with formaldehyde and a second shell layer covering the first shell layer and comprised of a condensation product of a phenolic compound with formaldehyde.

Description

  The present invention relates to particles for a display medium constituting a display medium used for an information display device that displays information such as images.

  A liquid crystal display (LCD) is widely used as an information display device. However, it is generally known that liquid crystal display devices have drawbacks such as large power consumption and narrow viewing angle. Therefore, as an alternative to the liquid crystal display device, a plurality of cells partitioned by a partition wall are formed between two substrates (for example, glass substrates) at least one of which is transparent, and the display medium is configured in the cells. There is a proposal for an information display device that encloses particles and displays an information such as an image by applying an electric field to the particles for display medium. Such an information display device has an advantage that power consumption can be significantly reduced because the display state can be maintained even if the drive power supply is turned off after display.

In the information display device as described above, whenever the information to be displayed changes, the display medium particles enclosed between the substrates are moved by applying an electric field. Therefore, the display medium particles to be employed are required to have a certain level of charging stability and durability. If the display medium particles less than the predetermined level are used, the display state becomes unstable, and the information display device cannot be trusted. For this reason, various studies have been made on display medium particles.
Therefore, conventionally, so-called composite display medium particles having a structure in which a large number of child particles are fixed to the surface of the mother particles have been studied. For example, Patent Document 1 proposes a technique for improving display stability by controlling the charge amount of child particles.

JP 2007-304409 A

  Patent Document 1 proposes a technique for improving the display state by improving the chargeability of composite particles composed of mother particles and child particles. However, in order to improve the display state in the information display device, not only the frictional charging property of the particles for the display medium but also the charge holding ability to hold the charged state for a certain time or more is substantially required. The display state cannot be improved. Furthermore, as described above, since there is a demand for durability, it is a fact that there are a plurality of problems to be examined for composite particles.

  Therefore, a main object of the present invention is to provide composite display medium particles for use in an information display device, in which the charge retention capability is improved and the triboelectric charge amount can be adjusted.

That is, the gist configuration of the present invention is as follows.
1. A display medium having optical reflectivity and chargeability is sealed between two substrates, at least one of which is transparent, and an electric field is applied to the display medium to move the gas space to display information such as an image. A display medium particle constituting the display medium for use in an information display device,
The display medium particles are formed as composite particles having child particles fixed to the surface of the mother particles, and the child particles are composed of a core portion and a shell portion covering the core portion,
The core part is composed of a condensate of a first amino compound essential to melamines and formaldehyde, and the shell part is composed of a condensate of a second amino compound essential to guanamines and formaldehyde. 1. A particle for a display medium, comprising: one shell layer; and a second shell layer covering the first shell layer and made of a condensate of a phenol compound and formaldehyde.

2. 2. The display medium particle according to 1 above, wherein the first amino compound essential for the melamines is melamine, and the second amino compound essential for the guanamines is benzoguanamine.

3. 3. The ratio of melamine in the first amino compound is 80 to 100% by mass, and the ratio of benzoguanamine in the second amino compound is 80 to 100% by mass. Particles for display media.

4). 4. The display medium according to any one of 1 to 3, wherein the average particle diameter of the mother particles is 1 to 20 μm, and the average particle diameter of the child particles is 0.1 to 1.0 μm. particle.

5. 5. The display medium particle according to any one of 1 to 4, wherein an external additive is further adhered to the surface of the composite particle.

6). 6. The display medium particle according to 5, wherein the external additive has a surface coverage of 100 to 1500%.

7). The said 2nd shell layer is content of the phenol compound in the 2nd shell layer with respect to the whole shell part being 1 mass% or more and 60 mass% or less, The said any one of 1-6 characterized by the above-mentioned. Particles for display media.

8). 8. The display medium particle according to any one of 1 to 7, wherein the display medium particle is subjected to a curing treatment.

9. 9. The display medium particle according to 8 above, wherein the curing treatment is a high-temperature pressurization treatment at a treatment temperature of 100 to 200 ° C. and a gas phase pressure of 0.1 to 5.0 MPa.

10. An information display device comprising the display medium particle according to any one of 1 to 9 above.

In the core-shell structure of the present invention, the core portion is composed of a condensate of the first amino compound and formaldehyde, which is essential for melamines, so that it has a high-order network structure and has shape stability, and the outer side is made of guanamines. Since it is covered with the first shell layer made of the condensate of the essential second amino compound and formaldehyde, the charge retention capability can be improved, and further, the second condensate of the phenol compound and formaldehyde. Since the shell layer is provided, the particles for display medium can be adjusted in the amount of triboelectric charge.
An information display device that employs such display medium particles can display information over a long period of time, and thus can be provided as a reliable display device.

(A), (b) is the figure shown in order to demonstrate the fundamental structure of the information display apparatus which can employ | adopt the particle | grains for display medium used as object. (A), (b) is the figure shown in order to demonstrate the other principle structure of the information display apparatus which can employ | adopt the particle | grains for display medium used as object. It is the figure shown about one structural example of the particle | grains for display media of this invention.

Hereinafter, an embodiment according to the present invention will be described in detail. The display medium particles constituting the display medium according to the present invention are encapsulated as a display medium having optical reflectivity and chargeability between two substrates, at least one of which is transparent. Then, by applying an electric field, the substrate is moved to display information such as an image.
In order to facilitate understanding of the present invention, a schematic configuration of an information display device that displays information such as an image using the display medium particles according to the present invention as a display medium will be described with reference to the drawings. In such an information display device, an electric field is applied to a display medium configured as a particle group including optical reflectance and chargeable particles sealed in a space between two opposing transparent substrates. Along with the applied electric field direction, the display medium is attracted by an electric field force or a Coulomb force, and the display medium is moved by a change in the electric field direction, whereby information such as an image is displayed. Therefore, it is necessary to design the information display device so that the display medium can be moved uniformly and the stability when the display information is rewritten repeatedly or when the display information is continuously displayed can be maintained. Here, as the force applied to the particles constituting the display medium, in addition to the force attracting each other by the Coulomb force between the particles, an electric mirror image force between the electrode and the substrate, an intermolecular force, a liquid cross-linking force, gravity and the like can be considered.

An example of an information display device that can employ particles for a display medium that is a subject of the present invention will be described with reference to FIGS. 1 (a), (b), 2 (a), and (b).
The examples shown in FIGS. 1A and 1B show at least two types of display media having different optical reflectance and charging characteristics, which are configured as a particle group including particles having at least optical reflectance and charging properties. (Shown here is a white display medium 3W configured as a particle group including negatively charged white particles 3Wa and a black display medium 3B configured as a particle group including positively charged black particles 3Ba). In each cell, an electric field generated by applying a voltage between an electrode pair formed by the electrode 5 (pixel electrode with TFT) provided on the substrate 1 and the transparent electrode 6 (common electrode) provided on the substrate 2 is applied. Accordingly, the substrate is moved perpendicularly to the substrates 1 and 2. Then, the white display medium 3W is visually recognized by the observer as shown in FIG. 1A, or white dots are displayed, or the black display medium 3B is visually recognized by the observer as shown in FIG. You can display. In addition, in FIG. 1 (a), (b), the partition in front is abbreviate | omitted.

  Further, in the example shown in FIGS. 2A and 2B, at least two types having different optical reflectivity and charging characteristics are configured as a particle group including particles having at least optical reflectivity and chargeability. The display medium (here, the white display medium 3W configured as a particle group including the negatively charged white particles 3Wa and the black display medium 3B configured as a particle group including the positively charged black particles 3Ba) is shown by the partition walls 4. In each formed cell, a voltage is applied between a pair of pixel electrodes formed by the electrode 5 (line electrode) provided on the substrate 1 and the transparent electrode 6 (line electrode) provided on the transparent substrate 2 at opposite orthogonal intersections. The substrate is moved perpendicularly to the substrates 1 and 2 in accordance with the electric field generated. Then, as shown in FIG. 2 (a), the white display medium 3W is visually recognized by the observer and white dot display is performed, or as shown in FIG. 2 (b), the black display medium 3B is visually recognized by the observer. Black dots are displayed. In addition, in FIG. 2 (a), (b), the partition in front is abbreviate | omitted. The electrodes 5 and 6 may be provided outside the substrates 1 and 2, inside the substrate, or embedded in the substrate. Although an example in which a pixel (dot) and a cell are associated with each other on a one-to-one basis is shown, the pixel and the cell may not be associated with each other.

  In addition, as said board | substrates 1 and 2, substrates, such as a glass substrate, a resin sheet board | substrate, and a resin film board | substrate, can be used. The substrate 2 on the display surface side (observation side) is a transparent substrate. When an electrode for applying a voltage having a predetermined voltage and polarity (positive / negative) (common electrode or line electrode 5 described in FIG. 1 or the like) is disposed in the information display screen area of the substrate 2 Is a transparent electrode. On the surface of the substrate 1 constituting the information display panel shown in FIGS. 1 and 2, pixel electrodes or line electrodes with thin film transistors (TFTs) are formed so as to form matrix electrode pairs. When a voltage is applied to the counter electrode pair, the above-described structure in which a desired display is performed by moving by applying an electric field to the display medium (particle group) can be realized.

Hereinafter, the composite type display medium particles in which the child particles are fixed to the surface of the base particles according to the present invention will be described in detail. The particles for a display medium of the present invention can be applied to the information display device of FIGS. 1 (a), 1 (b) and FIGS. 2 (a), 2 (b), at least one of which is transparent between two substrates. The display medium is configured and enclosed.
FIG. 3 is a diagram showing a structural example of the composite display medium particle according to the present invention. In the example shown in FIG. 3, the display medium particle 11 of the present invention includes a mother particle 12 and a large number of child particles 13 fixed to the surface of the mother particle 12.

The characteristic structure of the display medium particle according to the present invention is that the child particles fixed to the surface of the mother particle 12 cover the core portion 13a and the outside thereof as schematically shown in FIG. The shell portion 13b has a two-layer structure of a first shell layer 13b-1 and a second shell layer 13b-2. The core portion 13a is formed by a condensate of a first amino compound that essentially contains melamines and formaldehyde. The first shell layer 13b-1 is formed of a condensate of a second amino compound and formaldehyde, which essentially contains guanamines, and the second shell layer 13b-2 is a condensate of a phenol compound and formaldehyde. It is formed by.
Here, the core part on the center side is made of a condensate of formaldehyde and the first amino compound, which is essential for melamines, so it has a high-order network structure and has shape stability, so moderate durability and triboelectric charging are also achieved. However, functional groups such as methylol groups and amino groups remain. This functional group may cause a phenomenon in which charges are released after charging, which may reduce the charge holding ability.
However, since the outer side of the child particle of the composite display medium particle according to the present invention is covered with the first shell layer made of the condensate of the second amino compound and formaldehyde, which requires guanamines, charge decay Thus, the particles for a display medium can be obtained in which the charge retention capability is improved. Furthermore, in the present invention, the triboelectric charge amount can be adjusted according to the requirements by covering the first shell layer with the second shell layer made of a condensate of a phenol compound and formaldehyde.

Hereinafter, the particles for a display medium according to the present invention will be described in order.
First, the mother particles in the composite type particles will be described. The base particles include a pigment as a colorant in the base resin as a main component thereof, and may further include a charge control agent, an inorganic additive, and the like as necessary. Examples of resins, charge control agents, colorants, and other additives will be given below.

  Examples of base resin of base particles of display medium particles include urethane resin, urea resin, thiourethane resin, acrylic resin, polyester resin, acrylic urethane resin, acrylic thiourethane resin, acrylic urethane silicone resin, acrylic urethane fluororesin, Acrylic fluororesin, silicone resin, acrylic silicone resin, epoxy resin, polystyrene resin, styrene butadiene resin, styrene butadiene acrylic resin, styrene acrylic resin, polyolefin resin, polycycloolefin resin, norbornene resin, methylpentyl resin, butyral resin, vinylidene chloride Examples thereof include resins, melamine resins, phenol resins, fluororesins, polycarbonate resins, polysulfone resins, polyether resins, and polyamide resins. Two or more of these may be mixed and used. Moreover, what grind | pulverized the polymerized resin previously may be used, and what was formed by suspension polymerization may be used. When the charge control agent, the colorant, and other additives are kneaded and then pulverized, the main component of the mother particles must have thermoplasticity and be easily pulverized. From this viewpoint, for example, acrylic resins such as methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, Examples thereof include acrylic fluorine resins, polystyrene resins, styrene acrylic resins, polyolefin resins, polycycloolefin resins, norbornene resins, methylpentyl resins, and polystyrene resin hydrogenated products. In the case of suspension polymerization, an acrylic resin, an acrylic fluororesin, a polystyrene resin, a styrene acrylic resin, each hydrogenated product of a polystyrene resin, or the like is preferable because of its ease.

  The charge control agent is not particularly limited. Examples of the negative charge control agent include salicylic acid metal complexes, metal-containing azo dyes, metal-containing oil-soluble dyes (including metal ions and metal atoms), and quaternary ammonium salt systems. Examples thereof include compounds, calixarene compounds, boron-containing compounds (benzyl acid boron complexes), and nitroimidazole derivatives. Examples of the positive charge control agent include nigrosine dyes, triphenylmethane compounds, quaternary ammonium salt compounds, polyamine resins, imidazole derivatives, and the like. In addition, metal oxides such as ultrafine silica, ultrafine titanium oxide, ultrafine alumina, nitrogen-containing cyclic compounds such as pyridine and derivatives and salts thereof, various organic pigments, resins containing fluorine, chlorine, nitrogen, etc. are also charged. It can also be used as a control agent.

  As the colorant, various organic or inorganic pigments and dyes as exemplified below can be used. Examples of the black colorant include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon and the like. Examples of blue colorants include C.I. I. Pigment blue 15: 3, C.I. I. Pigment Blue 15, Bituminous Blue, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Metal-free Phthalocyanine Blue, Phthalocyanine Blue Partial Chlorides, Fast Sky Blue, Indanthrene Blue BC and the like. Examples of red colorants include bengara, cadmium red, red lead, mercury sulfide, cadmium, permanent red 4R, resol red, pyrazolone red, watching red, calcium salt, lake red D, brilliant carmine 6B, eosin lake, rhodamine lake B, Alizarin Lake, Brilliant Carmine 3B, C.I. I. Pigment Red 2 etc.

  Yellow colorants include yellow lead, zinc yellow, cadmium yellow, yellow iron oxide, mineral first yellow, nickel titanium yellow, navel yellow, naphthol yellow S, Hansa yellow G, Hansa yellow 10G, benzidine yellow G, and benzidine yellow. GR, Quinoline Yellow Lake, Permanent Yellow NCG, Tartrazine Lake, C.I. I. Pigment Yellow 12 etc. Examples of green colorants include chrome green, chromium oxide, pigment green B, C.I. I. Pigment Green 7, Malachite Green Lake, Final Yellow Green G, etc. Examples of the orange colorant include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, Indanthrene Brilliant Orange RK, Benzidine Orange G, Indanthren Brilliant Orange GK, C.I. I. Pigment Orange 31 etc. Examples of purple colorants include manganese purple, first violet B, and methyl violet lake. Examples of white colorants include zinc white, titanium oxide, antimony white, and zinc sulfide.

  Examples of extender pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white. Examples of various dyes such as basic, acidic, disperse, and direct dyes include nigrosine, methylene blue, rose bengal, quinoline yellow, and ultramarine blue.

Examples of inorganic additives include titanium oxide, zinc white, zinc sulfide, antimony oxide, calcium carbonate, lead white, talc, silica, calcium silicate, alumina white, cadmium yellow, cadmium red, cadmium orange, titanium yellow, Examples include bitumen, ultramarine blue, cobalt blue, cobalt green, cobalt violet, iron oxide, carbon black, manganese ferrite black, cobalt ferrite black, copper powder, and aluminum powder.
These pigments and inorganic additives can be used alone or in combination. Of these, carbon black is particularly preferable as the black pigment, and titanium oxide is preferable as the white pigment. By mixing the colorant, mother particles that are precursors of composite display medium particles can be produced with a desired color.

  Moreover, it is preferable that the average particle diameter d (0.5) of the mother particles in the display medium particles is in the range of 1 to 20 μm and is uniform and uniform. If the average particle diameter d (0.5) is larger than this range, the display is not clear. If the average particle diameter d (0.5) is smaller than this range, the cohesive force between the particles becomes too large, which hinders movement as a display medium.

Furthermore, in the present invention, regarding the particle size distribution of the mother particles in each display medium particle, the particle size distribution Span represented by the following formula is preferably less than 5, preferably less than 3.
Span = (d (0.9) −d (0.1)) / d (0.5)
(However, d (0.5) is a numerical value expressing the particle diameter in μm that 50% of the particles are larger than this and 50% is smaller than this, and d (0.1) is a particle in which the ratio of the smaller particles is 10%. (Numerical value expressed in μm, and d (0.9) is a numerical value expressed in μm for a particle diameter of 90% or less.)
By keeping Span within a range of 5 or less, the size of each particle is uniform, and movement as a uniform display medium becomes possible.

  Furthermore, in an information display panel using two types of display media composed of two types of display media particles having different charging polarities, the average grain of the display media having the larger average particle diameter d (0.5) It is important that the ratio between the diameter and the average particle diameter of the display medium having the smaller average particle diameter d (0.5) is 10 or less. Even if the particle size distribution Span is reduced, the display medium particles with different charging polarities move in the opposite directions, so the particle sizes of each other are the same, and the display medium particles move easily in the opposite directions. It is preferable to be able to do this, and this is the range.

The particle size distribution and the particle size can be obtained from a laser diffraction / scattering method or the like. When laser light is irradiated onto particles to be measured, a light intensity distribution pattern of diffracted / scattered light is spatially generated, and since this light intensity pattern has a corresponding relationship with the particle diameter, the particle diameter and particle diameter distribution can be measured. .
Here, the particle size and particle size distribution of the mother particles in the present invention are obtained from a volume-based distribution. For example, using a Mastersizer 2000 (Sysmex Corp.) measuring instrument, particles can be introduced into a nitrogen stream and the particle size and particle size distribution can be measured with the attached analysis software.
And about the child particle | grains demonstrated below fixed to the surface of the said mother particle, it is preferable to make the average particle diameter d (0.5) into the range of 0.1-1.0 micrometer. If it is larger than this range, there is an inconvenience that it becomes difficult to embed the child particles on the surface of the mother particle due to complexation, and if it is smaller than this range, it is difficult to control the embedding. Here, the coefficient of variation (CV value) of the child particles is preferably 30% or less. The coefficient of variation (CV value) can be determined by, for example, visually measuring the particle diameter using an image obtained by a scanning electron microscope (SEM). Here, it is preferable that the mother particle diameter is 1 to 20 μm and the child particle diameter is 0.1 to 1.0 μm.

As described above, the child particles fixed to the mother particles (see FIG. 3) are formed by adopting a novel core / shell structure which is not present in the prior art. The core / shell structure will be described in more detail below in the order of the core and the shell.
As for the 1st amino compound which comprises a core part, it is desirable for the ratio of a melamine to be 80-100 mass%. When the first amino compound contains a compound other than melamine (that is, when the proportion of melamine in the first amino compound is not 100% by mass), particularly about a compound that can be used as the first amino compound in addition to melamine There is no limit. For example, the compound is not particularly limited as long as it is a compound having an amino group in the molecule, but a compound having two or more amino groups in the molecule is preferable, and a polyfunctional amino compound having a triazine ring can be used more preferably. Examples of such polyfunctional amino compounds having a triazine ring include benzoguanamine (2,4-diamino-6-phenyl-sym-triazine), cyclohexenecarboguanamine, cyclohexenecarboguanamine, acetoguanamine, norbornenecarboguanamine, and spiroguanamine. A guanamine compound, a diaminotriazidine compound, etc. are mentioned.

Further, when a compound other than melamine is used as the first amino compound constituting the core part, only one such compound may be used, or two or more kinds may be used in combination.
In the positively charged particles of this embodiment, the core portion has a configuration including a condensate of the above-described first amino compound and formarted (H—C (═O) —H). The condensation reaction of a first amino compound such as melamine with formaldehyde is well known in the technical field relating to the synthesis of melamine resins. Specific reaction conditions and the like will be described later. In the first stage of the reaction, the amino group of the first amino compound such as melamine reacts with formaldehyde to form a methylol group (—CH ₂ OH) on the amino group. A group (for example, methylolmelamine) into which a group is introduced is produced. Then, in the second stage of the reaction, two of the compounds produced above react to cause one methylol group to be eliminated from one and a condensation reaction takes place. By repeating this, a condensate constituting the core is generated.

There is no restriction | limiting in particular about the shape of a core part, Arbitrary shapes, such as spherical shape, needle shape, plate shape, bowl shape, bowl shape, confetti shape, and indefinite shape, can be employ | adopted. Among these, a preferable core portion has a spherical shape.
Although there is no restriction | limiting in particular about the size of a core part, In the preferable form, the average particle diameter particle d of a core part is 0.01-0.5 micrometer. If the average particle size of the core part is within such a range, the thickness of the shell layer can be increased, and the average particle size as the core / shell particles can be controlled to a submicron size. There is. The average particle diameter d of the core part is more preferably 0.05 to 0.3 μm, further preferably 0.08 to 0.25 μm, and particularly preferably 0.1 to 0.2 μm. In the present invention, the average particle diameter d of the core portion was obtained by taking an SEM photograph so that the total number of particles was about 200, and the diameter of 100 particles randomly selected from the photograph (taken) The maximum diameter of the particles (gradual layer) is measured with a caliper, and the arithmetic average value is adopted as the average particle diameter.

Next, the shell part will be described.
First, the first shell layer will be described. By using a compound having a highly hydrophobic functional group such as an alkyl group or a phenyl group for the first shell layer, it is possible to have higher charge retention.
The ratio of benzoguanamine (2,4-diamino-6-phenyl-sym-triazine) in the second amino compound constituting the first shell layer is relatively high. More specifically, for example, in the positively charged particles, the ratio of benzoguanamine in the second amino compound is 80 to 100% by mass. This ratio is preferably 85 to 100% by mass, more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass, particularly preferably 98 to 100% by mass, and most preferably 100% by mass (that is, the total amount of the second amino compound is benzoguanamine). When the proportion of benzoguanamine in the second amino compound is within such a range, positively charged particles having excellent charge retention can be provided.

When the second amino compound constituting the first shell layer contains a compound other than benzoguanamine (that is, when the proportion of benzoguanamine in the second amino compound is not 100% by mass), the second amino compound other than benzoguanamine There is no restriction | limiting in particular about the compound which can be used as. However, to give an example, for example, the above-described guanamine compound (other than benzoguanamine) can be used.
In addition, compounds other than the guanamine compounds described above can also be used as the second compound constituting the first shell layer. Specifically, it is not particularly limited as long as it is a compound having an amino group in the molecule, but a compound having two or more amino groups in the molecule is preferable, and a polyfunctional amino compound having a triazine ring is more preferably used. sell. Examples of such a polyfunctional amino compound having a triazine ring include melamine and amino compounds other than melamine as described above, and diaminotriazine compounds as described above. When a compound other than benzoguanamine is used as the second amino compound constituting the shell layer of this embodiment, only one such compound may be used, or two or more may be used in combination.

The first shell layer includes a condensate of the above-described second amino compound and formaldehyde (H—C (= 0) —H). Since the condensation reaction between the second amino compound and formaldehyde and the form of the condensate obtained thereby are the same as those described above for the first amino compound, description thereof is omitted here.
There is no particular restriction as to the size of the first shell layer, in a preferred embodiment, the average thickness t ₁ of the shell layer is 0.01μm or more. When the average thickness of the shell portion is within such a range, positively charged particles that are sufficiently excellent in charge retention can be obtained. The average thickness t ₁ of the shell layer is more preferably 0.01 to 0.25 μm, still more preferably 0.02 to 0.15 μm, and particularly preferably 0.04 to 0.10 μm.

Next, the second shell layer will be described.
The second shell layer is composed of a condensate of a phenol compound and formaldehyde, and by controlling the coating amount, the size of the second shell layer is appropriately adjusted when the triboelectric charge amount by the first shell layer is too large. Can be adjusted.
Here, the “phenol compound” means a compound having a phenolic hydroxyl group. Although there is no restriction | limiting in particular about the specific form of a phenol compound, For example, phenol, o-ethylphenol, p-ethylphenol, mixed cresol, pn-propylphenol, o-isopropylphenol, p-isopropylphenol, mixed isopropyl Phenol, o-sec-butylphenol, m-tert-butylphenol, p-tert-butylphenol, benzylphenol, p-octylphenol, p-nonylphenol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,6- Dimethylphenol, 3,4-dimethylphenol, 2,4-di-s-butylphenol, 3,5-dimethylphenol, 2,6-di-s-butylphenol, 2,6-di-t-butylphenol, 3-methyl -4- Sopropylphenol, 3-methyl-5-isopropylphenol, 3-methyl-6-isopropylphenol, 2-t-butyl-4-methylphenol, 3-methyl-6-t-butylphenol, 2-t-butyl-4 -Compounds having a phenolic hydroxyl group such as ethylphenol, and compounds having two or more phenolic hydroxyl groups in the molecule, such as catechol, resocilun, biphenol, bisphenol A, bisphenol S, bisphenol F, and the like. Particularly preferred is phenol. As for these phenol compounds, only 1 type may be used independently and 2 or more types may be used together.

  Moreover, it is preferable to set it as 1 mass% or more about content of the phenolic compound in a 2nd shell layer with respect to the whole shell part, More preferably, it is 10 mass% or more. On the other hand, the upper limit value is preferably 60% by mass or less, more preferably 50% by mass or less, and more preferably 50% by mass or less, and the phenol compound is used if the content of the phenol compound is 1% by mass or more. This is preferable because the action and effect due to the occurrence of the problem can be sufficiently discovered. On the other hand, if the content of the phenol compound is 60% by mass or less, the high temperature compression deformation rate can be kept low, which is preferable.

  In the present invention, the second shell layer formed of a condensate of a phenol compound and formaldehyde can be formed by a conventionally known method while appropriately adjusting depending on the site where the phenol compound is desired to be contained. . For example, the phenol compound may be supplied to the reaction system at the same time as the second amino compound that requires guanamines, or may be supplied to the reaction system after supplying the second amino compound. Moreover, there is no restriction | limiting in particular also about the addition form of a phenol compound, Continuous dripping, division | segmentation addition, whole quantity lump addition, etc. can be selected suitably.

In the present invention, the average thickness t (t ₁ + t ₂ ) of the shell part is obtained when the average particle diameter of positively charged particles obtained by forming the shell part on the outer surface of the core part is D (μm). Using the average particle diameter d (μm) of the core described above, it can be calculated by t = (D−d) / 2. Moreover, in order to measure t directly from the state of positively charged particles, the caliper method described in Examples described later can be used.
Further, there is no particular limitation on the value of the ratio of the average thickness t of the shell part to the average particle diameter d of the core (t / d; also referred to as “shell part ratio”). However, in a preferred embodiment, the shell part ratio is 0.01-1. A shell part ratio in such a range is preferable in that the charge retention of positively charged particles is excellent. The shell ratio is more preferably 0.05 to 0.75, and particularly preferably 0.10 to 0.50.
The core-shell structure child particles detailed above have a structure with improved durability while maintaining a certain durability. A composite type particle formed by fixing such child particles to the surface of the base particle is a particle for a display medium having a required durability and an excellent charge characteristic. Core-shell structure child particles have a charge retention of 20 to 60% after voltage application, compared to conventional positively charged particles (charge retention after voltage application of 0 to 5%). Particles with excellent properties. The equilibrium weight average charge amount Q of the child particles is preferably 1.0 <Q <600 μC / g.

The core-shell structure child particles according to the present invention will be further described. The child particles are formed as positively charged particles.
(Positively charged particles)
The positively charged particles of the present embodiment are, as is apparent from the above description of the core part and the shell part, respectively, consisting of a condensate of an amino compound and formaldehyde as a whole, and the core part and the shell part each having a specific composition. It has the characteristics. Hereinafter, other preferable modes as the positively charged particles will be described.
The shape of the positively charged particles is not particularly limited, and any shape such as a spherical shape, a needle shape, a plate shape, a bowl shape, a scale shape, a scalloped sugar shape, and an indefinite shape, similar to the core portion described above, can be adopted. Of these, the shape of the positively charged particles is preferably spherical.
The size of the positively charged particles is not particularly limited, but in a preferred embodiment, the average particle diameter D of the positively charged particles is in the range of 0.1 to 1.0 μm. If the average particle diameter D of the positively charged particles is within such a range, the composite with the mother particles constituting the display medium particles can be performed uniformly. The average particle diameter D of the positive electrostatic particles is more preferably 0.1 to 0.8 μm, further preferably 0.15 to 0.5 μm, and particularly preferably 0.2 to 0.3 μm.
In the present invention, the average particle diameter D of the positively charged particles can be measured by the same measurement method as the average particle diameter d of the core part described above. The value of the coefficient of variation (CV) of the particle diameter of the positively charged particles is preferably 30% or less. If the CV value of the particle diameter of the positively charged particles is within such a range, it is preferable because stable charging performance can be achieved. The CV value of the particle diameter of the positively charged particles is more preferably 20% or less, and further preferably 15% or less. The CV value of the positively charged particles is a value calculated as a percentage (%) of the standard deviation of the particle diameter with respect to the average particle diameter D, and is an index indicating the degree of variation in the particle diameter of the positively charged particles. The smaller the value, the smaller the particle size variation.

(Method for producing positively charged core / shell particles)
There is no particular limitation on the method for producing the positively charged core / shell particles, and conventionally known knowledge can be appropriately referred to so that the positively charged particles having the above-described configuration can be obtained. Hereinafter, a preferred example of a method for producing the positively charged particles of the present embodiment will be described. However, the technical scope of the positively charged particles of the present embodiment is not affected by the production method described below.
In short, the positively charged particles are obtained by first condensing the first amino compound and formaldehyde in an aqueous solvent to produce a core portion containing the resulting condensate. Next, the obtained core part is dispersed in an aqueous medium, and the second amino compound and formaldehyde are added while heating, thereby condensing the second amino compound and formaldehyde on the outer surface of the core part. A first shell layer containing the resulting condensate is formed. Next, by covering the core portion having the first shell layer with a second shell layer made of a condensate of a phenol compound and formaldehyde, the shell portion made of the first shell layer and the second shell layer is covered. Form. As a result, positively charged particles can be produced. Hereinafter, it will be briefly described in the order of steps.

(Manufacture of core part)
In producing the core part, for example, a core part precursor is first obtained by subjecting a first amino compound and formaldehyde to a condensation reaction.
The raw materials used for producing the core part precursor are the first amino compound and formaldehyde. In order to produce the positively charged particles of the present invention, the ratio of melamine in the first amino compound may be 80 to 100% by mass. In addition, since it is as having mentioned above about the specific form of a 1st amino compound, detailed description is abbreviate | omitted here.
On the other hand, the formaldehyde used for the preparation of the core precursor may be in the form of an aqueous solution (ie, formalin), or in the form of an aqueous solution of a precursor that can generate formaldehyde in water, such as trioxa or paraformaldehyde. May be.
Subsequently, the core part precursor obtained above is mixed with a surfactant in an aqueous medium, and a curing catalyst is added to the mixed solution, and preferably heated. Thereby, a core part precursor is hardened and precipitated in an aqueous medium, and is granulated into a core part.

(Manufacture of shell part)
Subsequently, a first shell layer is formed on the outer peripheral portion of the core portion obtained above. For example, the first shell layer is formed on the outer peripheral portion of the core portion by, for example, dispersing the core portion obtained above in an aqueous medium and adding the second amino compound, preferably with formaldehyde, in the presence of a curing catalyst. The reaction system is heated. Thereby, a condensate of the second amino compound and formaldehyde grows on the outer peripheral portion of the core portion, and the first shell layer is formed.
Subsequently, the core part covered with the 1st shell layer obtained above is disperse | distributed to an aqueous medium, a phenol compound is added with a curing catalyst in the presence of a curing catalyst, and a reaction system is heated. As a result, a second shell layer made of a condensate of a phenol compound and formaldehyde is formed on the surface of the first shell layer.
Furthermore, in this invention, the hardening process with respect to a shell part can be given after said process. By this curing treatment, the shell portion is cured, thereby obtaining an effect that the particles are not deformed or adhered at the time of compounding.
Here, the above-described curing treatment is preferably a high-temperature pressurization treatment under conditions of treatment temperature: 100 to 200 ° C. and gas phase pressure: 0.1 to 5.0 MPa.
By the above-mentioned preferable production method, a reaction liquid in which positively charged particles having a core / shell structure are dispersed and contained in an aqueous medium can be obtained. From the reaction solution, particles are separated by a conventionally known separation method such as a centrifugal separation method, washed with a solvent as necessary, and dried to obtain powdered normal electric particles (positively charged particle powder). can get. When secondary charges of positively charged particles occur during drying, it is preferable to perform a conventionally known crushing treatment.

  Hereinafter, the external additive attached to the surface of the display medium particle will be described. In order to improve the fluidity of the composite particles, it is desirable to attach an external additive to the surface of the composite particles. External additives include silica, titania, alumina, yttria, calcium oxide, magnesium oxide, barium oxide, beryllium oxide, zinc oxide, tin oxide and other metal oxide based inorganic fine particles, and the above metal oxide with silicone oil, Other examples include surface-treated metal oxides chemically treated with HMDS, alkyltrialkoxysilanes, aminoalkyltrialkoxysilanes, etc., styrene-divinylbenzene-based crosslinked resin particles, acrylic-based crosslinked resin particles, cycloolefin-based crosslinked resin particles, etc. And fine particles constituting an external additive used in an electrophotographic toner. One or more of these external additives are preferably used. The particle diameter of the external additive is preferably 80 nm or less, more preferably 1 to 60 nm, and even more preferably 2 to 40 nm. The surface coverage of the external additive is desirably 100 to 1500%. Since the external additive has a strong cohesive force, a more preferable coverage is 300 to 1000% in order to uniformly coat the composite particle surface. Here, the surface coverage is determined to be 200% or 300% when two or three layers are formed, assuming that the state in which the external additive is uniformly attached to the surface of the display medium particles is 100%. Is.

  Below, each member which comprises the information display panel using the particle | grains for composite type display media by this invention is demonstrated further.

  As the substrate described above, at least one of the substrates is a transparent substrate on which the color of the display medium can be confirmed from the outside of the panel, and a material having high visible light transmittance and good heat resistance is preferable. The back substrate as the other substrate may be transparent or opaque. Examples of the substrate material include organic polymer substrates such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene (PE), polycarbonate (PC), polyimide (PI), polyethersulfine (PES), and acrylic. Alternatively, a glass sheet, a quartz sheet, a metal sheet, or the like is used, and a transparent one is used on the display surface side. The thickness of the substrate is preferably 2 to 2000 μm, more preferably 5 to 1000 μm. If it is too thin, it will be difficult to maintain the strength and the uniformity of the distance between the substrates, and if it is thicker than 2000 μm, it will be a thin information display panel. It becomes inconvenient.

If necessary, the electrode forming material provided on the substrate may be made of metals such as aluminum, silver, nickel, copper, and gold, indium tin oxide (ITO), indium zinc oxide (IZO), zinc aluminum oxide (AZO). And conductive metal oxides such as indium oxide, conductive tin oxide, antimony tin oxide (ATO), and conductive zinc oxide, and conductive polymers such as polyaniline, polypyrrole, and polythiophene. Can be used. As a method for forming the electrode, a method of patterning the above-exemplified materials into a thin film by sputtering, vacuum deposition, CVD (chemical vapor deposition), coating, or the like, or a method of laminating metal foil (for example, rolled copper foil) Method) and a method of forming a pattern by mixing a conductive agent with a solvent or a synthetic resin binder and applying it.
The electrodes provided on the information display screen region of the viewing side (display surface side) substrate need to be transparent, but the electrodes provided outside the information display screen region and on the back side substrate do not need to be transparent. In any case, the above-mentioned material that is conductive and capable of pattern formation can be suitably used. In addition, the electrode thickness should just be sufficient if electroconductivity is ensured and there is no trouble in light transmittance, and 0.01-10 micrometers, Preferably 0.05-5 micrometers is suitable. The material and thickness of the electrode provided on the back side substrate are the same as those of the electrode provided on the display surface side substrate described above, but need not be transparent.

The shape of the partition provided on the substrate is appropriately set according to the type of display medium involved in display, the shape and arrangement of the electrodes to be arranged, and is not generally limited. However, the width of the partition is 2 to 100 μm, preferably 3 ~ 50 μm. The height of the partition wall can be within the inter-substrate gap, the substrate gap securing portion being the same as the inter-substrate gap, and the other cell forming portions being the same or lower than the inter-substrate gap. In forming the partition wall, a both-rib method in which ribs are formed on each of the opposing substrates 1 and 2 and then bonded, and a single-rib method in which ribs are formed only on one substrate are conceivable. In the present invention, any method is preferably used. The height of the partition wall is adjusted to the distance between the substrates, but may be partially lower than the distance between the substrates.
The cells formed by the partition walls made of these ribs are exemplified by, for example, a square shape, a triangular shape, a line shape, a circular shape, and a hexagonal shape as viewed from the plane of the substrate. The shape is illustrated. It is better to make the portion corresponding to the cross section of the partition wall visible from the display surface side (the area of the cell frame portion) as small as possible, and the clearness of the display state can be increased.
Examples of the method for forming the partition include a mold transfer method, a screen printing method, a sand blast method, a photolithography method, and an additive method. Any of these methods can be suitably used for an information display panel mounted on the information display device of the present invention, and among these, a photolithography method using a resist film and a mold transfer method are preferably used.

Furthermore, in a dry information display panel in which a display medium composed of display medium particles is driven in a gas space, it is important to manage the gas in the gap surrounding the display medium between the substrates, which contributes to improved display stability. To do. Specifically, it is important that the relative humidity at 25 ° C. is 60% RH or less, preferably 50% RH or less with respect to the humidity of the gas in the void portion.
1A, 1B, 2A, and 2B, the gaps are defined as electrodes 5 and 6 (electrodes on the substrate). In the case of being provided on the inner side), a gas portion in contact with a so-called display medium excluding an occupied portion of the display medium 3, an occupied portion of the partition wall 4, and a seal portion of the information display panel is meant. The gas in the gap is not limited as long as it is in the humidity region described above, but dry air, dry nitrogen, dry argon, dry helium, dry carbon dioxide, dry methane, and the like are preferable. This gas needs to be sealed in an information display panel so that the humidity is maintained, for example, filling a display medium, assembling an information display panel, etc. in a predetermined humidity environment, It is important to apply a sealing material and a sealing method that prevent moisture from entering from the outside.

The distance between the substrate in the information display panel in which the particles for a display medium according to the present invention are adopted is only required to be able to move the display medium and maintain the contrast, but is usually 10 to 500 μm, preferably 10 to 200 μm. In the information display panel of the charged particle movement type, the thickness is adjusted to 10 to 100 μm, preferably 10 to 50 μm.
The volume occupation ratio of the display medium in the gas space between the opposing substrates is preferably 5 to 70%, more preferably 5 to 60%. Note that if it exceeds 70%, the movement of the display medium is hindered, and if it is less than 5%, the contrast tends to be unclear.

(Example)
Examples of the display medium particles according to the present invention will be described below.
The particle diameter was taken using a JEOL transmission electron microscope (JSM-7500F) so that the total number of particles was about 200, and the diameter of 100 particles randomly selected from the photograph ( The maximum particle diameter of the photographed particles (gradation layer) was measured with a caliper, and the arithmetic average was measured as the average particle diameter.
The triboelectric charge amount was measured using the following apparatus based on the general flow-off method under the following conditions.
Measuring device: Blow-off type charge measurement machine (Kyocera Chemical Co., Ltd., TB-203)
Mesh aperture: 32 [μm]
Blow pressure / Suction pressure: 4.5 [kPa] /9.5 [kPa]
Carrier: F96-80 (Powder Tech)
Shaking frequency: 1000 times The charge retention amount of the display medium particles was measured under the following conditions.
(1) Fill a copper cell with a layer having a layer thickness of 300 (μm).
(2) Scorotron charger (needle applied voltage ± 10 (kV), grid voltage ± 1 (kV))
Thus, an electric charge is applied so that the particle surface potential is ± 1 (kV).
(3) Connected to ground (GND) and started measurement at room temperature (22 ° C) and humidity (50RH%).
The charge retention (%) was obtained by dividing the surface potential after 4 hours by the initial surface potential.
(4) The charge retention was judged to be high if the charge retention rate of the composite particles was 80 (%) or higher.
The fluidity of the display medium particles was measured under the following conditions.
Measuring device: Powder tester (Hosokawa Micron Co., Ltd .: PT-R type)
3 g of particles are weighed and gently placed on a 32 μm sieve. The weight of particles remaining on the sieve after vibrating for 2 minutes at 1 mm amplitude (residue residue weight) was weighed, and the fluidity was determined from the following equation. The lower the value, the better the fluidity.
Fluidity (%) = (initial weight−sieving residue weight) / initial weight × 100

Composite display medium particles were produced as display medium particles to be sealed in the display medium device. The composite particles are produced by biaxially using 100 parts by mass of cycloolefin polymer (TOPAS: manufactured by Polyplastics Co., Ltd.) and 5 parts by mass of carbon black (SPECIAL BLACK4: manufactured by Evonik-Degussa Co., Ltd.) as mother particles for black display media. The mixture was kneaded and pulverized and classified with a jet mill (Lab Jet Mill IDS-LJ type: Nippon Pneumatic Co., Ltd.) to obtain an average particle size of 10 μm.
The white display medium particles are obtained by biaxially kneading 100 parts by mass of cycloolefin polymer (TOPAS: manufactured by Polyplastics Co., Ltd.) and 100 parts by mass of titanium dioxide (Taipaque CR-50: manufactured by Ishihara Sangyo Co., Ltd.). By pulverizing and classifying with a jet mill (Lab Jet Mill IDS-LJ type: manufactured by Nippon Pneumatic Co., Ltd.), an average particle size of 10 μm was obtained.

Subsequently, the composite particles were produced by compositing the mother particles and the child particles under the following conditions so that the child particles were adhered and fixed to the surface layer of the mother particles.
A compounding device (Nobil Tamil (NOB-130): Hosokawa Micron Corporation) was used. In this apparatus, a rotatable stirring blade is provided in a container, and mother particles and child particles are compacted between the stirring blade and the inner surface of the container, and shear force is applied to the mother particles and child particles existing therebetween. It has a configuration to give. Processing was performed so that the input energy was 2400 kJ.
The external additive is applied by mixing the composite particles in advance with an amount of external additive that gives a predetermined coverage, and then stirring the carbon mixer processor (manufactured by SMT Corporation: HFM-001C) at 4000 rpm. The treatment was performed so that the external additive was uniformly applied to the particle surface.

As described below, core-shell structured particles were prepared, and their chargeability and charge retention were confirmed.
[Production Example 1]
(Formation of core part)
In a four-necked 2 L separable flask equipped with a stirrer, a reflux condenser and a thermometer, 400 parts by mass of melamine, 772 parts by mass of 37% by mass formalin, and 12 parts by mass of 25% by mass aqueous ammonia are stirred and heated. Separately adjusted solid content concentration 65 mass% sodium dodecylbenzenesulfonate aqueous solution (Neopelex G65: Kao Corporation: hereinafter, also simply referred to as “DBSNa”) 25.2 parts by mass, and ion-exchanged water 5600 mass Thereafter, 200 parts by mass of a 10% by mass aqueous solution of dodecylbenzenesulfonic acid (hereinafter also simply referred to as “DBS”) was added thereto. This state was maintained for 5 hours to obtain 7009.2 parts by mass of a liquid containing amino resin crosslinked particles (1) (hereinafter also simply referred to as “melamine resin seed liquid (1)”). In addition, when the average particle diameter of the amino resin crosslinked particles (1) contained in the melamine resin seed solution (1) was measured, it was 0.19 μm and the CV value was 12.0%.
(Formation of shell part)
(Formation of benzoguanamine resin coating layer)
200 parts by mass of benzoguanamine (hereinafter also simply referred to as “BG”), 260 parts by mass of 37% by mass formalin, 12.6 parts by mass of DBSNa, 10 parts by mass of DBS, and 2770.3 parts by mass of ion-exchanged water are uniformly dispersed and mixed. Thus, a BG dispersion was obtained. And the said BG dispersion liquid was dripped in 4177.8 mass parts of melamine resin seed liquid (1) adjusted above, and also it hold | maintained for 5 hours after completion | finish of dripping. As a result, the dispersion (1) containing the BG-coated amino resin crosslinked particles (1) having the surface of the amino resin crosslinked particles (1) coated with a condensate of BG and formaldehyde (hereinafter simply referred to as “BG coated slurry ( 1) ")) 7430.7 parts by mass were obtained.
(Formation of phenolic resin coating layer)
Phenol (hereinafter also referred to as “PhOH”) 50 parts by mass, 37% by mass formalin 129.7 parts by mass, 65% by mass DBSNa 3.2 parts by mass, DBS 2.5 parts by mass, and ion-exchanged water 815 parts by mass Were uniformly dispersed and mixed to obtain a PhOH-dispersed aqueous solution. Then, the above PhOH dispersion aqueous solution is dropped into 7430.7 parts by mass of the melamine resin seed solution (1) adjusted as described above, and is further maintained for 5 hours after the dropping is completed. Dispersion liquid (1) containing PhOH / BG-coated amino resin crosslinked particles (1) whose surface of amino resin crosslinked particles (1) is coated with a condensate of PhOH and formaldehyde (hereinafter simply referred to as “PhOH / BG-coated slurry”). 8431.1 parts by mass (also referred to as “(1)”) was obtained.
(Pressure-Wash-Dry-Grind)
8000 parts by mass of the PhOH / BG-coated slurry (1) obtained above and 24 parts by mass of a curing catalyst (Catanit A: made by MRC Unitech) were charged into a 10 L pressure vessel and heated while stirring. Heat treatment was performed at a temperature of 170 ° C. to obtain a high-temperature pressure-treated PhOH / BG-coated slurry (1). The obtained high-temperature pressure-treated PhOH / BG-coated slurry (1) was subjected to solid-liquid separation with a centrifuge, the supernatant was removed, and the sedimented cake was taken out. After the obtained cake was dispersed in methanol, an operation of performing solid-liquid separation with a centrifuge was repeated twice to obtain a cake washed with methanol. The obtained cake was vacuum-dried at 190 ° C. for 3 hours, and the obtained dry powder was pulverized to obtain PhOH / BG-coated amino resin-crosslinked particles (1) as positively charged particles.
The PhOH / BG-coated amino resin crosslinked particles (1) have an average particle diameter of 0.25 μm, a CV value of 7.3%, a compression deformation rate of 21.9%, a triboelectric charge amount of 42.8 μC / g, and charge retention. The rate was 53.7%.

[Production Examples 2 to 5]
(Formation of core part)
In the same manner as in Production Example 1 described above, a liquid containing amino resin crosslinked particles (2) to (5) composed of a condensate of melamine and formaldehyde with the average particle diameter and CV value shown in Table 1 (hereinafter referred to as dispersion) The benzoguanamine resin coating layers and phenols were prepared by simply preparing “melamine resin seed solutions (2) to (5)” and changing the amounts of benzoguanamine and phenol (mass ratio) relative to the amount of melamine as shown in Table 1. Resin coating layers were sequentially formed to produce dispersions (2) to (5) containing PhOH / BG-coated amino resin crosslinked particles (2) to (5). Thereafter, in the same manner as in Production Example 1, pressure, washing, drying, and pulverization were performed to obtain PhOH / BG-coated amino resin crosslinked particles (2) to (5).

[Comparative Production Example 1]
Eposter S (manufactured by Nippon Shokubai Co., Ltd.) was prepared as a melamine crosslinked particle which is one kind of positively charged particles. The average particle diameter of the melamine resin crosslinked particles was 0.20 μm, the CV value was 12.4%, the triboelectric charge was 129.0 μC / g, and the charge retention was 0.0%.
The physical property results of each particle are shown in Table 1 below.

  As shown in Table 1, all the particles of Production Examples 1 to 5 show a higher charge retention and a lower saturated moisture absorption amount as compared with Comparative Production Example 1.

[Example 1]
(Production of composite particles)
The composite particles are composed of cycloolefin polymer spherical particles having an average particle diameter of 9 μm as mother particles and PhOH / BG-coated amino resin crosslinked particles (1) as child particles, and a composite device (Novirtamil (NOB-130): Hosokawa Micron) And manufactured so that the input energy is 2400 kJ. No deformation of the particles due to the composite was observed. The composite type particle (1) has a triboelectric charge amount of 29.8 μC / g and a charge retention rate of 94.6%, exhibits a positive charge, has a charge amount necessary for driving, and has a high charge retention rate. Indicated.

[Examples 2 to 5]
(Production of composite particles)
Composite particles (2) to (5) were produced in the same manner as in Example 1 except that PhOH / BG-coated amino resin crosslinked particles (2) to (5) were used as the child particles. No deformation of the particles due to the composite was observed.

[Comparative Example 1]
(Production of composite particles)
Composite particles (6) were produced in the same manner as in Example 1 except that melamine crosslinked particles were used as the child particles. The composite particles (6) had a triboelectric charge amount of 29.0 μC / g and a charge retention rate of 63.2%, which showed positive charge and had a charge amount necessary for driving. Was low.
The physical property results of each particle are shown in Table 2 below.

  As shown in Table 2, all of Examples 1 to 5 achieved a higher charge retention rate than Comparative Example 1. In addition, as the phenol coverage increases, the triboelectric charge tends to decrease, indicating that the triboelectric charge can be adjusted according to the phenol coverage.

[Example 6]
100 g of composite type particles prepared in Example 5 and 1.7 g of external additive (HDK H3050VP: WACKER) (mixing ratio: 250%) were mixed in advance, and then a carbon mixer processor (manufactured by SMT Co., Ltd .: HFM-). 001C) was stirred at 4000 rpm, and a treatment was performed so that the external additive was uniformly applied to the surface of the composite particles, thereby producing particles (1) for black display media. The fluidity of the black display medium particles (1) was 5.1%, indicating a high fluidity.

[Example 7]
Particles for black display medium were obtained in the same manner as in Example 6 except that 100 g of the composite type particles prepared in Example 5 and 3.3 g of external additive (HDK H3050VP: WACKER) (coverage: 500%) were used. 2) was produced. The fluidity of the black display medium particles (2) was 5.2%, which showed high fluidity.

[Example 8]
The same procedure was performed as in Example 6 except that 100 g of composite type particles prepared in Example 5 and 4.8 g of external additive (HDK H3050VP: WACKER) (coverage 750%) were used. 3) was produced. The fluidity of the black display medium particles (3) was 5.0%, indicating a high fluidity.

[Example 9]
Particles for black display medium were obtained in the same manner as in Example 6 except that 100 g of composite type particles prepared in Example 5 and 6.6 g of external additive (HDK H3050VP: WACKER) (coverage rate 1000%) were used. 4) was produced. The fluidity of the black display medium particles (4) was 5.3%, which showed high fluidity.

[Comparative Example 2]
The composite type particles produced in Example 5 were used as black display medium particles (5) without performing the external additive coating treatment. The fluidity was 22.3%, which was worse than the particles for black display media subjected to the external additive treatment.

[Comparative Example 3]
Particles for black display medium (6) were obtained in the same manner as in Example 2 except that 100 g of the composite particles prepared in Comparative Example 1 and 6.6 g of external additive (HDK H3050VP: WACKER) (coverage rate 1000%) were used. ) Was produced. The particles for black display medium (6) had a fluidity of 5.9% and exhibited high fluidity.
The physical property results of each particle are shown in Table 3 below.

The panel is manufactured by combining the particles for white display medium and the particles for black display medium, which are prepared as described above, and the particle filling amount is 5 g / m ² between the panels on which the transparent electrodes (ITO) are formed. A filled evaluation panel was prepared. The panel used this time has an electrode-to-electrode distance of 40 μm, and an electric field of 2 × 10 ⁶ (V / m) is applied to the display medium particles when a voltage of 80 V is applied.

Evaluation of the panel performed white display and black display on the evaluation panel by applying a voltage of 80 V between the electrodes of the evaluation panel while changing the direction of the voltage. And in each of white display and black display, the OD value (optical density) was measured using an optical densitometer (Sakata Inx Engineering Co., Ltd .: RD19I). Based on OD: ODW for white display and OD: BOD for black display, contrast CR = 10 ^(BOD-WOD) was calculated and used as an index of panel performance. The case where CR at the time of 80V drive was CR> 5 was determined to be acceptable (◯), and the case where CR ≦ 5 was determined to be unacceptable (x). In addition, a voltage was applied at an interval of 10 minutes, and a case where CR was CR> 5 was determined to be acceptable (◯), and a case where CR ≦ 5 was determined to be unacceptable (x).

(Panel evaluation results)
Black display medium particles (1) to (6) prepared in Examples 6 to 9 and Comparative Examples 2 and 3, white display medium particles (white display medium mother particles and silica (Seahosta-S30: Nippon Shokubai ( Panel) was evaluated by combining external particles (HDK H3004: manufactured by WACKER Co., Ltd.) with a composite type particle) and a composite type particle).
The evaluation results are shown in Table 3.

The black display medium particles (1) to (4) showed good contrast at 80 V drive, 10 minute drive, and 30 minute drive.
The particles for black display medium (5) were not driven and did not show good contrast.
The black display medium particles (6) showed good contrast when driven at 80 V, but the particles were not driven when driven at 10-minute intervals, and good contrast was not obtained.

In the composite type display medium particles described above, the child particles fixed on the surface of the mother particles are formed in a core-shell structure, and the core part is composed of a first amino compound and formaldehyde whose melamines are essential. The outer shell portion is formed of a first shell layer made of a condensate of a second amino compound and formaldehyde, which essentially contains guanamines, and a condensate of a phenol compound and formaldehyde. And a second shell layer. The composite type display medium particles including such child particles can improve the charging stability while having the necessary durability, and can also adjust the triboelectric charge amount. And if it is set as the form which further made the external additive adhere to the surface, it will become the particle | grains for display media which improved fluidity | liquidity and was more excellent.
An information display device that employs such display medium particles can be provided as a reliable display device that can display information stably and stably over a long period of time.

  Information display devices using the particles for display media of the present invention include notebook computers, electronic notebooks, portable information devices called PDA (Personal Digital Assistants), display units for mobile devices such as mobile phones and handy terminals, and electronic books. , Electronic papers such as electronic newspapers, signboards, posters, bulletin boards such as blackboards (whiteboards), electronic desk calculators, home appliances, automobile supplies, etc., card displays such as point cards, IC cards, electronic advertisements, information In addition to the display section of boards, electronic POPs (Point Of Presence, Point Of Purchase advertising), electronic price tags, electronic shelf labels, electronic musical scores, and RF-ID devices, the display section of various electronic devices such as POS terminals, car navigation devices, watches, etc. Preferably used. In addition, it is also suitably used as a rewritable paper (which can be rewritten using an external electric field forming means).

DESCRIPTION OF SYMBOLS 1, 2 Substrate 3W White display medium 3Wa Negatively charged white particle 3B Black display medium 3Ba Positively charged black particle 4 Partition 5 and 6 Electrode 11 Display medium particle 12 Base particle 13 Child particle 13a Core part 13b Shell part 13b-1 First shell layer 13b-2 Second shell layer

Claims (10)

A display medium having optical reflectivity and chargeability is sealed between two substrates, at least one of which is transparent, and an electric field is applied to the display medium to move the gas space to display information such as an image. A display medium particle constituting the display medium for use in an information display device,
The display medium particles are formed as composite particles having child particles fixed to the surface of the mother particles, and the child particles are composed of a core portion and a shell portion covering the core portion,
The core part is composed of a condensate of a first amino compound essential to melamines and formaldehyde, and the shell part is composed of a condensate of a second amino compound essential to guanamines and formaldehyde. 1. A particle for a display medium, comprising: one shell layer; and a second shell layer covering the first shell layer and made of a condensate of a phenol compound and formaldehyde.   The display medium particle according to claim 1, wherein the first amino compound essential to the melamines is melamine, and the second amino compound essential to the guanamines is benzoguanamine.   The ratio of melamine in the first amino compound is 80 to 100% by mass, and the ratio of benzoguanamine in the second amino compound is 80 to 100% by mass. Particles for display media.   4. The display medium according to claim 1, wherein an average particle diameter of the mother particles is 1 to 20 μm, and an average particle diameter of the child particles is 0.1 to 1.0 μm. Particles.   5. The display medium particle according to claim 1, wherein an external additive is further adhered to the surface of the composite particle.   6. The display medium particle according to claim 5, wherein a surface coverage of the external additive is 100 to 1500%.   The content of the phenol compound in the second shell layer in the second shell layer with respect to the whole shell portion is 1% by mass or more and 60% by mass or less, according to any one of claims 1 to 6. Particles for display media.   The display medium particle according to claim 1, wherein the display medium particle is subjected to a curing treatment.   9. The display medium particle according to claim 8, wherein the curing treatment is a high-temperature pressurization treatment at a treatment temperature of 100 to 200 [deg.] C. and a gas phase pressure of 0.1 to 5.0 MPa.   An information display device comprising the display medium particle according to claim 1.