JP6810413B1 - Microcapsule magnetic electrophoresis display that can be erased from the recording surface side - Google Patents
Microcapsule magnetic electrophoresis display that can be erased from the recording surface side Download PDFInfo
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Classifications
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/165—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on translational movement of particles in a fluid under the influence of an applied field
- G02F1/166—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on translational movement of particles in a fluid under the influence of an applied field characterised by the electro-optical or magneto-optical effect
- G02F1/1673—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 magnetophoresis
-
- 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
- G02F1/16757—Microcapsules
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- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
【課題】 消去性、コントラストに優れ、耐久性、安全性、画質の優れた薄型化を可能とした表面から消去可能なマイクロカプセル磁気泳動ディスプレーを提供する。【解決手段】 光吸収性磁性体粒子と光反射性非磁性体粒子の二成分を油性分散媒中に分散した分散液をマイクロカプセルに封入して基板上に配列し、基板外部より印加する磁場によって分散媒中の二成分をマイクロカプセル内においてその位置を移動させて白色上に黒色の文字または像等の磁気記録表示体を表示し、または消去することを特徴とする表面から消去可能なマイクロカプセル磁気泳動ディスプレーにおいて、光吸収性磁性体粒子として平均粒径０．５μｍ以下のマグネタイトと平均粒径１．０μｍ以下のハードフェライト粒子の２種または数種を組み合わせて用いた。【選択図】なしPROBLEM TO BE SOLVED: To provide a microcapsule magnetic electrophoresis display capable of erasable from a surface, which is excellent in erasability and contrast, and has excellent durability, safety and image quality and can be thinned. SOLUTION: A dispersion liquid in which two components of light-absorbing magnetic particles and light-reflecting non-magnetic particles are dispersed in an oil-based dispersion medium is enclosed in microcapsules, arranged on a substrate, and a magnetic field applied from outside the substrate. Erasable from the surface, characterized in that the two components in the dispersion medium are moved in position within the microcapsules to display or erase magnetic recording indicators such as black letters or images on white. In the capsule magnetic migration display, two or several types of magnetite having an average particle size of 0.5 μm or less and hard ferrite particles having an average particle size of 1.0 μm or less were used as light-absorbing magnetic particles. [Selection diagram] None
Description
本発明は、記録表面側から消去可能なマイクロカプセル磁気泳動ディスプレーに関する。 The present invention relates to a microcapsule magnetic electrophoresis display that can be erased from the recording surface side .
マイクロカプセル磁気泳動ディスプレーは特許文献１以降商品化され知られている。マイクロカプセル磁気泳動ディスプレーは、光吸収性磁性体粒子と光反射性非磁性体粒子の二成分および添加剤を油性分散媒中に分散した分散液をマイクロカプセルに封入して基板上に配列し、基板外部より印加する磁場によって分散媒中の二成分をマイクロカプセル内においてその位置を移動させて、白色上に黒色の文字または像の磁気記録表示体を表示し、または消去するようにした筆記用具の一種である。 Microcapsule magnetic electrophoresis displays have been commercialized and known since Patent Document 1. In the microcapsule magnetic migration display, a dispersion liquid in which two components of light-absorbing magnetic particles and light-reflecting non-magnetic particles and additives are dispersed in an oil-based dispersion medium is encapsulated in microcapsules and arranged on a substrate. A writing tool that moves the positions of two components in a dispersion medium in a microcapsule by a magnetic field applied from outside the substrate to display or erase a magnetic recording display of black characters or images on white. It is a kind of.
マイクロカプセル磁気泳動ディスプレーは、記録表面に表示された磁気記録表示体を消去する場合、一般に、基板の記録裏面側を消去用磁石でスライドさせることにより行っている。しかし、このような消去作業は手間がかかり、また、磁気記録表示体の一部だけを消去するといったことができない。 When erasing a magnetic recording display body displayed on the recording surface, the microcapsule magnetic electrophoresis display is generally performed by sliding the recording back surface side of the substrate with an erasing magnet. However, such erasing work is troublesome, and it is not possible to erase only a part of the magnetic recording display body.
このような問題を解決するためには、基板の記録表面側から記録表面に表示された磁気記録表示体を消去できるようにすることが望ましい。
基板の記録表面側から記録表面に表示された磁気記録表示体を消去できるものとして、特許文献２に、上消し可能なマイクロカプセル磁気泳動表示シート、消去用磁石並びに筆記用磁石が開示されている。
In order to solve such a problem, it is desirable to be able to erase the magnetic recording display body displayed on the recording surface from the recording surface side of the substrate.
Patent Document 2 discloses a microcapsule magnetic migration display sheet, an erasing magnet, and a writing magnet that can be erased from the recording surface side of the substrate so that the magnetic recording display body displayed on the recording surface can be erased. ..
特許文献２のマイクロカプセル磁気泳動表示シートは、光吸収性磁性体粒子として、粒径が異なる光吸収性磁性体粒子を２種以上有している。また、消去用磁石は、マイクロカプセル磁気泳動表示シートと磁石との間にクリアランスが生じるように磁石を配置することにより、磁石を直接シート上に接触させた時とは異なる磁界がシートのマイクロカプセルに作用するようになっている。 The microcapsule magnetic migration display sheet of Patent Document 2 has two or more kinds of light-absorbing magnetic particles having different particle sizes as light-absorbing magnetic particles. In addition, the erasing magnet has a magnetic field different from that when the magnet is brought into direct contact with the sheet by arranging the magnet so that a clearance is generated between the microcapsule magnetic electrophoresis display sheet and the magnet. It is designed to act on.
特許文献２にあって、マイクロカプセル磁気泳動表示シートの記録表面側から磁気記録表示体を消去した場合、光吸収性磁性体粒子はマイクロカプセルの中心付近に分散または凝集するが、シート表面と光吸収性磁性体粒子との距離を確保して隠蔽力を出すためにも光吸収性磁性体粒子の平均粒径は小さいほど効果的であり、また、平均粒径が小さいほど比表面積が大きくなることから少ない量で黒色度を高めることができ、シャープさやコントラストの優れた磁気記録表示体を表示できる。しかし、光吸収性磁性体粒子の平均粒径が小さいと、磁場印加時の可動性（磁気泳動スピード）は劣る。 In Patent Document 2, when the magnetic recording display is erased from the recording surface side of the microcapsule magnetic migration display sheet, the light-absorbing magnetic particles are dispersed or aggregated near the center of the microcapsule, but the sheet surface and light The smaller the average particle size of the light-absorbing magnetic particles, the more effective it is in order to secure the distance from the absorbent magnetic particles and to exert the hiding power, and the smaller the average particle size, the larger the specific surface area. Therefore, the blackness can be increased with a small amount, and a magnetic recording display body having excellent sharpness and contrast can be displayed. However, if the average particle size of the light-absorbing magnetic particles is small, the mobility (magnetic migration speed) when a magnetic field is applied is inferior.
他方、光吸収性磁性体粒子の平均粒径が大きいほど磁場印加時の可動性に優れ、消去性を高めることができる。しかし、マイクロカプセルに占める光吸収性磁性体粒子の体積は大きくなりシート表面と光吸収性磁性体粒子との距離が小さくなり隠蔽力は低下し、白色度が劣ことになる。その結果磁気記録表示体のシャープさやコントラストは犠牲になり、ディスプレーシートの薄型化のためにマイクロカプセルの粒径を小さくするとコントラストの低下はさらに顕著となってしまう。 On the other hand, the larger the average particle size of the light-absorbing magnetic particles, the better the mobility when a magnetic field is applied, and the higher the erasability. However, the volume of the light-absorbing magnetic particles in the microcapsules becomes large, the distance between the sheet surface and the light-absorbing magnetic particles becomes small, the hiding power decreases, and the whiteness becomes inferior. As a result, the sharpness and contrast of the magnetic recording display are sacrificed, and if the particle size of the microcapsules is reduced in order to reduce the thickness of the display sheet, the decrease in contrast becomes more remarkable.
特許文献２では、光吸収性磁性体粒子として、粒径が異なる光吸収性磁性体粒子を２種以上有しており、大粒径の光吸収性磁性体粒子が泳動する際に、小粒径の光吸収性磁性体粒子を吸引して小粒径の光吸収性磁性体粒子の動きを補助、促進するように働き、磁場印加時の可動性を高めるとともに、磁気記録表示体のシャープさやコントラストの低下を抑えるようにしているが、いずれか一方を向上させようとすると他方が低下することになり、消去性とコントラスト性の双方を満足させるものとはならないといった問題がある。 In Patent Document 2, as the light-absorbing magnetic particles, two or more kinds of light-absorbing magnetic particles having different particle sizes are provided, and when the large-particle light-absorbing magnetic particles run, they are small particles. It works by attracting light-absorbing magnetic particles of diameter to assist and promote the movement of light-absorbing magnetic particles of small particle size, increasing mobility when a magnetic field is applied, and sharpening the magnetic recording display. Although the decrease in contrast is suppressed, if one is tried to be improved, the other is decreased, and there is a problem that both the erasability and the contrast are not satisfied.
また、使用の多様化に伴い、ディスプレーシートの薄型化が求められており、このためにマイクロカプセルの粒径を小さくすると、大粒径の光吸収性磁性体粒子により、マイクロカプセルに占める光吸収性磁性体粒子の体積は大きくなり、コントラストの低下はさらに顕著となってしまうといった問題があった。 In addition, with the diversification of use, it is required to make the display sheet thinner. Therefore, when the particle size of the microcapsules is reduced, the light absorption occupying the microcapsules due to the large particle size of the light-absorbing magnetic particles. There is a problem that the volume of the sexual magnetic particles becomes large and the decrease in contrast becomes more remarkable.
さらには、特許文献２には、磁性粒子として粒径が０．１μｍ〜１．０μｍの範囲で１種以上とこれより粒径の大きい１μｍを超え２０μｍまでの範囲で１種以上からなる、粒径が異なる磁性粒子を２種以上有することを特徴とする開示があるが、粒径の大きい磁性粒子をすべてのマイクロカプセルに行き渡らせるには、その使用量が多くなり粒径の大きい、高比重の磁性粒子を各マイクロカプセルに均一に封入することは困難であるといった、製造上の問題があった。 Further, in Patent Document 2, one or more kinds of magnetic particles having a particle size in the range of 0.1 μm to 1.0 μm and one or more kinds in the range of more than 1 μm and up to 20 μm having a larger particle size are included. There is a disclosure characterized by having two or more kinds of magnetic particles having different diameters, but in order to distribute magnetic particles having a large particle size to all microcapsules, the amount used is large and the particle size is large and the specific gravity is high. There is a manufacturing problem that it is difficult to uniformly enclose the magnetic particles of the above in each microcapsule.
本発明の目的は、消去性、コントラストに優れ、耐久性、安全性、画質の優れた薄型化を可能とした記録表面側から消去可能なマイクロカプセル磁気泳動ディスプレーを提供することにある。 An object of the present invention is to provide a microcapsule magnetic electrophoresis display that can be erased from the recording surface side , which is excellent in erasability and contrast, and has excellent durability, safety, and image quality and can be made thin.
上記の目的を達成するため、請求項１に記載の発明は、光吸収性磁性体粒子と光反射性非磁性体粒子の二成分を油性分散媒中に分散した分散液をマイクロカプセルに封入して基板上に配列し、基板外部より印加する磁場によって分散媒中の二成分をマイクロカプセル内においてその位置を移動させて白色上に黒色の文字または像の磁気記録表示体を表示し、または消去することを特徴とする記録表面側から消去可能なマイクロカプセル磁気泳動ディスプレーにおいて、光吸収性磁性体粒子として平均粒径０．５μｍ以下のマグネタイトと平均粒径１．０μｍ以下のハードフェライト粒子の２種を組み合わせて用いたことを特徴とする。 In order to achieve the above object, the invention according to claim 1 encloses a dispersion liquid in which two components of light-absorbing magnetic particles and light-reflecting non-magnetic particles are dispersed in an oil-based dispersion medium in microcapsules. The two components in the dispersion medium are moved in the microcapsules by the magnetic field applied from the outside of the substrate to display or erase the magnetic recording display of black characters or images on white. In a microcapsule magnetic migration display that can be erased from the recording surface side, two types of light-absorbing magnetic particles are magnetite having an average particle size of 0.5 μm or less and hard ferrite particles having an average particle size of 1.0 μm or less. It is characterized by using a combination of seeds .
請求項１に記載の発明によれば、光吸収性磁性体粒子として平均粒径０．５μｍ以下のマグネタイトと平均粒径１．０μｍ以下のハードフェライト粒子の２種を組み合わせて用いたので、マイクロカプセル磁気泳動表示シートの記録表面側から磁気記録表示体を消去した場合、光吸収性磁性体粒子の平均粒径は小さいので、マイクロカプセルの中心付近に分散または凝集した光吸収性磁性体粒子と基板表面との距離が確保でき、光反射性非磁性体粒子による隠蔽力が高く、また、平均粒径が小さいので比表面積が大きく、少ない量で黒色度を高めることができ、シャープさやコントラストの優れた磁気記録表示体を表示できる。
また、磁場を印加したとき、ハードフェライト粒子が磁化され、ハードフェライト粒子の残留磁化によりマグネタイトを引きつけて密凝集し、見掛け大粒径の光吸収性磁性体粒子となり、磁場印加時の可動性が高くなり、消去性を高めることができる。
また、光吸収性磁性体粒子の平均粒径が小さく、そして少ない量で黒色度を高めることができるので、光吸収性磁性体粒子を各マイクロカプセルに均一に封入することが容易となる。
According to the invention of claim 1, two types of light-absorbing magnetic particles, magnetite having an average particle size of 0.5 μm or less and hard ferrite particles having an average particle size of 1.0 μm or less, are used in combination. When the magnetic recording display is erased from the recording surface side of the capsule magnetic migration display sheet, the average particle size of the light-absorbing magnetic particles is small, so that the light-absorbing magnetic particles dispersed or aggregated near the center of the microcapsule are used. A distance from the substrate surface can be secured, the hiding power of light-reflecting non-magnetic particles is high, and since the average particle size is small, the specific surface area is large, and the blackness can be increased with a small amount, resulting in sharpness and contrast. It can display an excellent magnetic recording display.
In addition, when a magnetic field is applied, the hard ferrite particles are magnetized, and the residual magnetization of the hard ferrite particles attracts and densely aggregates magnetite, resulting in apparently large particle size light-absorbing magnetic particles, which makes them mobile when a magnetic field is applied. It becomes high and the erasability can be improved.
Further, since the average particle size of the light-absorbing magnetic particles is small and the blackness can be increased with a small amount, it becomes easy to uniformly enclose the light-absorbing magnetic particles in each microcapsule.
請求項２に記載の発明は、請求項１に記載の記録表面側から消去可能なマイクロカプセル磁気泳動ディスプレーにおいて、
前記マイクロカプセルに封入した分散液が
（１）油性分散媒が引火点７０℃以上であり１５℃における体積密度が０．７５〜０．９１ｇ／ｃｍ3であり、４０℃における動粘度が７ｍｍ2／ｓ以下である一種または数種の混合油状液体であり、
（２）上記（１）の油性分散媒には、ＨＬＢ値が５．０以下の常温下で液状である非イオン界面活性剤を０．５〜８．０重量％を含有せしめたものであり、
（３）前記分散液の画像形成素子分散後の体積密度が、画像形成素子である光吸収性磁性体と光反射性非磁性体の双方の混合粒子を用いて１．０〜１．２ｇ／ｃｍ3に調整されたことを特徴とする。
The invention according to claim 2 is the microcapsule magnetic electrophoresis display that can be erased from the recording surface side according to claim 1.
The dispersion liquid encapsulated in the microcapsules is (1) the oil-based dispersion medium has a flash point of 70 ° C. or higher, a volume density of 0.75 to 0.91 g / cm 3 at 15 ° C., and a kinematic viscosity of 7 mm 2 at 40 ° C. One or several mixed oily liquids of / s or less,
(2) The oily dispersion medium of (1) above contains 0.5 to 8.0% by weight of a nonionic surfactant which is liquid at room temperature with an HLB value of 5.0 or less. ,
(3) The volume density of the dispersion liquid after dispersion in the image-forming element is 1.0 to 1.2 g / g using mixed particles of both a light-absorbing magnetic material and a light-reflecting non-magnetic material, which are image-forming elements. It is characterized by being adjusted to cm 3 .
請求項２に記載の発明によれば、体積密度の低い物性の分散媒を用いても高収率のマイクロカプセルが製造可能となり、分散媒の引火点、体積密度、動粘度以外にもマイクロカプセル磁気泳動ディスプレーの性能に関わる融点、屈折率などの選択肢が拡がり、より安全性の高い分散媒が使用可能となり、従来よりもコントラスト、耐久性、安全性の優れた記録表面側から消去可能なマイクロカプセル磁気泳動ディスプレーを得ることができる。
さらに、マイクロカプセルに封入する分散液の体積密度を画像形成素子で調整することにより、マイクロカプセルの粒径を小さくすると生じるコントラストの低下を極限までに低減することができるため、ディスプレー面の平滑度、物理的な耐圧強度と印字画質に優れた薄型化の適性を具えた、記録表面側から消去可能なマイクロカプセル磁気泳動ディスプレーを得ることができる。
According to the invention of claim 2, high-yield microcapsules can be produced even by using a dispersion medium having a low volume density and physical properties, and microcapsules other than the ignition point, volume density, and kinematic viscosity of the dispersion medium can be produced. Options such as melting point and refractive index related to the performance of the magnetic migration display have been expanded, a more safe dispersion medium can be used, and micro-encapsulation that can be erased from the recording surface side , which has better contrast, durability, and safety than before. A capsule magnetic migration display can be obtained.
Furthermore, by adjusting the volume density of the dispersion liquid enclosed in the microcapsules with an image forming element, the decrease in contrast caused by reducing the particle size of the microcapsules can be reduced to the utmost limit, and thus the smoothness of the display surface. It is possible to obtain a microcapsule magnetic migration display that can be erased from the recording surface side , which has excellent physical pressure resistance and print image quality and is suitable for thinning.
請求項３に記載の発明は、請求項１または２に記載の記録表面側から消去可能なマイクロカプセル磁気泳動ディスプレーにおいて、前記油性分散媒がノルマルパラフィン類、イソパラフィン類、ナフテン類の一種または数種の混合物であることを特徴とする。 The invention according to claim 3 is a microcapsule magnetic electrophoresis display that can be erased from the recording surface side according to claim 1 or 2, wherein the oily dispersion medium is one or several kinds of normal paraffins, isoparaffins, and naphthenes. It is characterized by being a mixture of.
請求項３に記載の発明によれば、前記油性分散媒がノルマルパラフィン類、イソパラフィン類、ナフテン類の一種または数種の混合物であるので、分散媒としての安全性と、マイクロカプセル磁気泳動ディスプレーの耐久性、マイクロカプセル内での磁気泳動性に優れた分散液を得ることができる。 According to the invention of claim 3, since the oily dispersion medium is one or a mixture of normal paraffins, isoparaffins, and naphthenes, the safety as a dispersion medium and the microcapsule magnetic electrophoresis display It is possible to obtain a dispersion having excellent durability and magnetic mobility in microcapsules.
以上のように構成された本発明によれば、より消去性、コントラストの優れた記録表面側から消去可能なマイクロカプセル磁気泳動ディスプレーを得ることができる。 According to the present invention configured as described above, it is possible to obtain a microcapsule magnetic electrophoresis display that can be erased from the recording surface side having better erasability and contrast.
以下は、本発明に係る記録表面側から消去可能なマイクロカプセル磁気泳動ディスプレーの実施の形態を説明するが、本発明はこれに限定されるものではない。 Hereinafter, embodiments of a microcapsule magnetic electrophoresis display that can be erased from the recording surface side according to the present invention will be described, but the present invention is not limited thereto.
本発明に係る記録表面側から消去可能なマイクロカプセル磁気泳動ディスプレーは、光吸収性磁性体粒子と光反射性非磁性体粒子の二成分および添加剤を油性分散媒中に分散した分散液をマイクロカプセルに封入して基板上に配列し、基板外部より印加する磁場によって分散媒中の二成分をマイクロカプセル内においてその位置を上下に移動させて白色上に黒色の文字または像等の磁気記録表示体を表示し、または消去することを特徴とする記録表面側から消去可能なマイクロカプセル磁気泳動ディスプレーにおいて、光吸収性磁性体粒子として平均粒径０．５μｍ以下のマグネタイトと平均粒径１．０μｍ以下のハードフェライト粒子の２種を組み合わせて用いている。 The microcapsule magnetic migration display that can be erased from the recording surface side according to the present invention is a micro-dispersion liquid in which two components of light-absorbing magnetic particles and light-reflecting non-magnetic particles and additives are dispersed in an oil-based dispersion medium. It is encapsulated and arranged on a substrate, and the two components in the dispersion medium are moved up and down in the microcapsule by a magnetic field applied from outside the substrate to display magnetic records such as black letters or images on white. In a microcapsule magnetic migration display that can be erased from the recording surface side, which is characterized by displaying or erasing the body, magnetite having an average particle size of 0.5 μm or less and an average particle size of 1.0 μm as light-absorbing magnetic particles. The following two types of hard ferrite particles are used in combination.
本発明において、光吸収性磁性体粒子として用いているマグネタイトは、従来のマイクロカプセル磁気泳動ディスプレーにも用いられている。 In the present invention, magnetite used as light-absorbing magnetic particles is also used in a conventional microcapsule magnetic electrophoresis display.
マグネタイトにあっては、その平均粒径が小さいほど比表面積は大きくなることから少ない量で黒色度を高めることができるものの、平均粒径が小さいと磁場印加時の可動性（磁気泳動スピード）は劣るものであった。
マグネタイトの平均粒径を大きくすると、磁場印加時の可動性が向上するが、マイクロカプセル磁気泳動ディスプレーを記録表面側から消去した場合、光吸収性磁性体粒子はマイクロカプセルの中心付近に分散または凝集するものの、マイクロカプセルに占めるマグネタイトの体積は大きくなり記録表面とマグネタイトとの距離が小さくなるため隠蔽力は低下し、白色度が劣りコントラストの低下の要因となってしまうことになる。
In the case of magnetite, the smaller the average particle size, the larger the specific surface area, so the blackness can be increased with a small amount, but if the average particle size is small, the mobility (magnetic migration speed) when a magnetic field is applied becomes high. It was inferior.
Increasing the average particle size of magnetite improves mobility when a magnetic field is applied, but when the microcapsule magnetic migration display is erased from the recording surface side , the light-absorbing magnetic particles are dispersed or aggregated near the center of the microcapsules. However, since the volume of magnetite in the microcapsules becomes large and the distance between the recording surface and magnetite becomes small, the hiding power is lowered, the whiteness is deteriorated, and the contrast is lowered.
また、本発明において、マグネタイトとともに光吸収性磁性体粒子として用いているハードフェライト粒子は平均粒径が小さくても磁場印加時の可動性が極めて良く、記録表面側からの消去でも優れた消去性が得られるものであるが、ハードフェライト粒子のみでは黒色度が不足するため、白色上に黒色の文字または像の磁気記録表示体を良好に表示することができない。 Further, in the present invention, the hard ferrite particles used as light-absorbing magnetic particles together with magnetite have extremely good mobility when a magnetic field is applied even if the average particle size is small, and have excellent erasability even when erased from the recording surface side . However, since the blackness is insufficient only with the hard ferrite particles, it is not possible to satisfactorily display the magnetic recording display body of black characters or images on white.
本発明は、光吸収性磁性体粒子として、黒色度の高いマグネタイトと磁場印加時の可動性が極めて良いハードフェライト粒子とを組合せて用いることにより、平均粒径の小さいマグネタイトの使用を可能にし、黒色度を向上させてコントラストの優れた記録表面側から消去可能なマイクロカプセル磁気泳動ディスプレーが得られるようにした。
本発明では、平均粒径０．５μｍ以下のマグネタイトを使用しているが、０．３μｍ以下のマグネタイトが好ましい。
The present invention enables the use of magnetite having a small average particle size by using a combination of magnetite having a high degree of blackness and hard ferrite particles having extremely good mobility when a magnetic field is applied as light-absorbing magnetic particles. The blackness was improved so that a microcapsule magnetite display that can be erased from the recording surface side with excellent contrast can be obtained.
In the present invention, magnetite having an average particle size of 0.5 μm or less is used, but magnetite having an average particle size of 0.3 μm or less is preferable.
マグネタイトとハードフェライト粒子の量比については、各粒子の平均粒径、ハードフェライト粒子の磁気特性、マイクロカプセルの粒径により選択、調節すれば良い。 The amount ratio of magnetite to hard ferrite particles may be selected and adjusted according to the average particle size of each particle, the magnetic characteristics of the hard ferrite particles, and the particle size of the microcapsules.
このように、本発明では光吸収性磁性体粒子として、黒色度の高いマグネタイトと磁場印加時の可動性が極めて良いハードフェライト粒子とを組合せて用いるので、光吸収性磁性体粒子が小さく配合量が少なくても黒色度を高めることができることに加えて、マイクロカプセル磁気泳動ディスプレーを記録表面側から消去した場合ハードフェライト粒子の残留磁化が大きいためマグネタイトはハードフェライトの磁力に引き付けられてマイクロカプセルの中心付近に密に凝集するので記録表面と光吸収性磁性体粒子との距離が大きくなり隠蔽力が高まり白色度も優れ、コントラストの優れた記録表面側から消去可能なマイクロカプセル磁気泳動ディスプレーが得られる。 As described above, in the present invention, as the light-absorbing magnetic particles, magnetite having a high degree of blackness and hard ferrite particles having extremely good mobility when a magnetic field is applied are used in combination, so that the light-absorbing magnetic particles are small and the blending amount is small. In addition to being able to increase the blackness even if the amount is small, when the microcapsule magnetic field display is erased from the recording surface side , the residual magnetization of the hard ferrite particles is large, so the magnetite is attracted to the magnetic force of the hard ferrite and is attracted to the microcapsule. Since it aggregates densely near the center, the distance between the recording surface and the light-absorbing magnetic particles is increased, the hiding power is enhanced, the whiteness is excellent, and a microcapsule magnetic migration display that can be erased from the recording surface side with excellent contrast is obtained. Be done.
また本発明では、光吸収性磁性体粒子の平均粒径が小さく、そして少ない量で黒色度を高めることができるので、光吸収性磁性体粒子を各マイクロカプセルに均一に封入することが容易となる。 Further, in the present invention, since the average particle size of the light-absorbing magnetic particles is small and the blackness can be increased with a small amount, it is easy to uniformly enclose the light-absorbing magnetic particles in each microcapsule. Become.
また、光吸収性磁性体粒子と光反射性非磁性体粒子の二成分および添加剤を油性分散媒中に分散したマイクロカプセルに封入される分散液にあっては、（１）油性分散媒が引火点７０℃以上であり、１５℃における体積密度が０．７５〜０．９１ｇ／ｃｍ３であり、４０℃における動粘度が７ｍｍ２/ｓ以下である一種または数種の混合油状液体であり、（２）上記（１）の油性分散媒には、ＨＬＢ値が５．０以下の常温下で液状である非イオン界面活性剤を０．５〜８．０重量％を含有せしめたものであり、（３）前記分散液の画像形成素子分散後の体積密度が、画像形成素子である光吸収性磁性体と光反射性非磁性体の双方の混合粒子を用いて１．０〜１．２ｇ／ｃｍ３に調整されて成る。 Further, in the dispersion liquid enclosed in the microcapsules in which the two components of the light-absorbing magnetic particles and the light-reflecting non-magnetic particles and the additive are dispersed in the oil-based dispersion medium, (1) the oil-based dispersion medium is used. It is a mixed oily liquid of one or several kinds having a flammability point of 70 ° C. or higher, a volume density of 0.75 to 0.91 g / cm3 at 15 ° C., and a kinematic viscosity of 7 mm2 / s or less at 40 ° C. 2) The oil-based dispersion medium of (1) above contains 0.5 to 8.0% by weight of a nonionic surfactant that is liquid at room temperature with an HLB value of 5.0 or less. (3) The volume density of the dispersion liquid after dispersion in the image-forming element is 1.0 to 1.2 g / g using mixed particles of both a light-absorbing magnetic material and a light-reflecting non-magnetic material, which are image-forming elements. It is adjusted to cm3.
分散液を上記のように調整することにより、体積密度の低い物性の分散媒を用いても高収率のマイクロカプセルが製造可能となり、分散媒の引火点、体積密度、動粘度以外にもマイクロカプセル磁気泳動ディスプレーの性能に関わる融点、屈折率などの選択肢が拡がり、より安全性の高い分散媒が使用可能となり、従来よりもコントラスト、耐久性、安全性の優れた記録表面側から消去可能なマイクロカプセル磁気泳動ディスプレーが得られる。 By adjusting the dispersion liquid as described above, high-yield microcapsules can be produced even if a dispersion medium having low volume density is used, and microcapsules other than the ignition point, volume density, and kinematic viscosity of the dispersion medium can be produced. Options such as melting point and refractive index related to the performance of the capsule magnetic migration display have been expanded, a more safe dispersion medium can be used, and it can be erased from the recording surface side , which has better contrast, durability, and safety than before. A microcapsule magnetic migration display is obtained.
さらにマイクロカプセルに封入する分散液の体積密度を画像形成素子で調整することにより、マイクロカプセルの粒径を小さくすると生じるコントラストの低下を極限までに低減できるため、ディスプレー面の平滑度、物理的な耐圧強度と印字画質に優れた薄型化の適性を具えた、記録表面側から消去可能なマイクロカプセル磁気泳動ディスプレーを得ることができる。 Furthermore, by adjusting the volume density of the dispersion liquid encapsulated in the microcapsules with an image forming element, the decrease in contrast caused by reducing the particle size of the microcapsules can be reduced to the utmost limit, so that the smoothness and physical appearance of the display surface can be reduced. It is possible to obtain a microcapsule magnetic migration display that can be erased from the recording surface side , which has excellent pressure resistance and print image quality and is suitable for thinning.
また、分散液で使用される油性分散媒としては、安全性、マイクロカプセル磁気泳動ディスプレーの耐久性、マイクロカプセル内での磁気泳動性といった面から、ノルマルパラフィン類、イソパラフィン類、ナフテン類の一種または数種の混合物であることが好ましい。 The oily dispersion medium used in the dispersion is a kind of normal paraffins, isoparaffins, naphthenes or a kind of normal paraffins, isoparaffins, naphthenes from the viewpoints of safety, durability of microcapsule magnetic migration display, and magnetic mobility in microcapsules. It is preferably a mixture of several types.
また、本発明に用いられる光反射性非磁性体粒子、各種添加剤は公知のものが使用できる。
また、本発明のマイクロカプセル内包液の分散、マイクロカプセルの形成および不溶化処理、水系インク組成物の製法および材料、塗布方法、非磁性体基板、乾燥または硬化方法については公知の方法、物質が使用できる。
磁気泳動による文字や像形成のための磁場印加については公知のペン状磁石や公知の電磁石磁気ヘッドも使用可能である。
消去については公知の消去用磁石で記録表面側から消去も可能で、公知の方法でディスプレーの記録裏面側から消去することもできる。
Further, known light-reflecting non-magnetic particles and various additives can be used in the present invention.
In addition, known methods and substances are used for the dispersion of the microcapsule inclusion liquid of the present invention, the formation and insolubilization treatment of microcapsules, the manufacturing method and material of the water-based ink composition, the coating method, the non-magnetic substrate, and the drying or curing method. it can.
A known pen-shaped magnet or a known electromagnet magnetic head can also be used for applying a magnetic field for forming characters or images by magnetic electrophoresis.
Regarding erasing, it is possible to erase from the recording front side with a known erasing magnet, and it is also possible to erase from the recording back side of the display by a known method.
以下実施例及び比較例により本発明を具体的に説明するが、本発明はこれらによって限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
［実施例１］
〔マイクロカプセル内包分散液の配合〕
分散媒（ナフテンベースオイル）６８．８重量％
界面活性剤（ソルビタントリオレエート）３．７重量％
ハードフェライト粒子（バリウムフェライト、平均粒径０．８μｍ）０．９重量％
マグネタイト（平均粒径０．２μｍ）１．６重量％
光反射性非磁性体粒子（二酸化チタン）２０．８重量％
沈降防止剤（疎水化シリカナノ粒子）１．７重量％
添加剤（酸化防止剤、消泡剤等）２．５重量％
[Example 1]
[Combining of dispersion containing microcapsules]
Dispersion medium (naphthenic base oil) 68.8% by weight
Surfactant (Sorbitan trioleate) 3.7% by weight
Hard ferrite particles (barium ferrite, average particle size 0.8 μm) 0.9% by weight
Magnetite (average particle size 0.2 μm) 1.6% by weight
Light-reflecting non-magnetic particles (titanium dioxide) 20.8% by weight
Anti-settling agent (hydrophobicized silica nanoparticles) 1.7% by weight
Additives (antioxidants, defoamers, etc.) 2.5% by weight
上記マイクロカプセル内包分散液を公知のコンプレックスコアセルベーション法で平均粒径２００μｍのゼラチン皮膜マイクロカプセル化し、公知の硬化剤で硬化し、２９７μｍおよび４５μｍメッシュスクリーンで分級し４５〜２９７μｍマイクロカプセルを得た。
得られたマイクロカプセルスラリーを脱水しバインダーとして公知の樹脂エマルションを加え消泡剤、増粘剤等の添加剤を加え水系インク組成物を作製した。
マットハードコート表面処理をした１００μｍ厚みのＰＥＴフィルムに４００μｍ厚みで水系インク組成物を塗布し送風乾燥後、片面粘着加工３８μＰＥＴフィルムとラミネートしマイクロカプセル磁気泳動ディスプレー試験片を作製した。
The microcapsule-encapsulated dispersion was microencapsulated with a gelatin film having an average particle size of 200 μm by a known complex coagulation method, cured with a known curing agent, and classified with a 297 μm and 45 μm mesh screen to obtain 45 to 297 μm microcapsules. ..
The obtained microcapsule slurry was dehydrated, a resin emulsion known as a binder was added, and additives such as a defoaming agent and a thickener were added to prepare a water-based ink composition.
A water-based ink composition having a thickness of 400 μm was applied to a 100 μm-thick PET film that had been surface-treated with a matte hard coat, dried by blowing air, and then laminated with a single-sided adhesive-processed 38 μm PET film to prepare a microcapsule magnetic electrophoresis display test piece.
［比較例１］
実施例１のハードフェライト粒子に変えて合成酸化鉄、平均粒径３μｍを用いたほかは同様にマイクロカプセル磁気泳動ディスプレー試験片を作製した。
[Comparative Example 1]
A microcapsule magnetic electrophoresis display test piece was prepared in the same manner except that synthetic iron oxide and an average particle size of 3 μm were used instead of the hard ferrite particles of Example 1.
［比較例２］
実施例１のハードフェライト粒子に変えてカルボニル鉄粉、平均粒径５μｍを用いたほかは同様にマイクロカプセル磁気泳動ディスプレー試験片を作製した。
[Comparative Example 2]
A microcapsule magnetic migration display test piece was prepared in the same manner except that carbonyl iron powder and an average particle size of 5 μm were used instead of the hard ferrite particles of Example 1.
［比較例３］
実施例１のマグネタイト、平均粒径０．２μｍのものに変えて平均粒径０．６μｍのものを用いたほかは同様にマイクロカプセル磁気泳動ディスプレー試験片を作製した。
[Comparative Example 3]
A microcapsule magnetic electrophoresis display test piece was prepared in the same manner except that the magnetite of Example 1 was used instead of the one having an average particle size of 0.2 μm and the one having an average particle size of 0.6 μm was used.
［比較例４］
特許文献２の実施例１で入手できなかった分散剤ノプコサントＫ９６３に変えてソルビタントリオレエートを用いたほかは同様の配合でマイクロカプセル内包分散液を作製し、実施例１の製法でマイクロカプセル磁気泳動ディスプレー試験片を作製した。
[Comparative Example 4]
A microcapsule-encapsulated dispersion was prepared with the same composition except that sorbitan trioleate was used instead of the dispersant Nopcosant K963, which was not available in Example 1 of Patent Document 2, and microcapsule electrophoresis was performed by the production method of Example 1. A display test piece was prepared.
実施例及び比較例で作製した試験片について以下の方法で評価を行った。
＜白色度＞
各試験片の表面および裏面を５５０Ｇ．２．４ｍｍピッチ片面多極ゴム磁石で各３回走査し表面を白色の状態にした。
分光濃度計エックスライト５０４を用いて白色度の測定を行った。
＜黒色度＞
表面が白色の状態である各試験片を電動板上に置き、０．８ｍｍ径長さ１ｍｍの１３９０Ｇ．ネオジウム磁石の周囲にヨークを取り付け、その周囲に前記磁石１２個をＳ極とＮ極が交互になるように設置し、その外周にもヨークを取り付けた５ｍｍ径の磁気ペンが試験片に対して垂直になるよう設置し、試験片とともに電動板を１８９ｍｍ／秒で動かし黒色の線を描画した。
各試験片の黒色の線を描画した部分を分光濃度計エックスライト５０４を用いて黒色度の測定を行った。
＜消去性＞
黒色の線を描画した各試験片を電動板上に置き、電動板の上方２４ｍｍに設置した回転軸に９８０Ｇ．フェライト磁石を組み込みモーターで回転させ、試験片とともに電動板を９４ｍｍ／秒で動かし３回通過させ表面からの消去性を確認した。
＜消去後の白色度＞
表面から消去できた試験片については表面から消去した場合の白色度を分光濃度計エックスライト５０４を用いて測定を行った。
＜コントラスト＞
消去後の白色度と黒色度との差であるコントラストを算出した。
The test pieces prepared in Examples and Comparative Examples were evaluated by the following methods.
<Whiteness>
The front and back surfaces of each test piece were 550 G. The surface was made white by scanning three times with a 2.4 mm pitch single-sided multi-pole rubber magnet.
The whiteness was measured using the spectrophotometer X-Rite 504.
<Blackness>
Each test piece having a white surface was placed on an electric plate, and the diameter was 0.8 mm and the length was 1 mm. A yoke is attached around the neodymium magnet, 12 magnets are installed around it so that S poles and N poles alternate, and a 5 mm diameter magnetic pen with a yoke attached to the outer circumference is attached to the test piece. It was installed vertically, and the electric plate was moved at 189 mm / sec together with the test piece to draw a black line.
The blackness of each test piece on which the black line was drawn was measured using the spectrophotometer X-Rite 504.
<Erasability>
Each test piece with a black line drawn was placed on the electric plate, and 980 G.A. was placed on a rotating shaft installed 24 mm above the electric plate. A ferrite magnet was incorporated and rotated by a motor, and the electric plate was moved at 94 mm / sec together with the test piece and passed three times to confirm the erasability from the surface.
<Whiteness after erasing>
For the test piece that could be erased from the surface, the whiteness when erased from the surface was measured using a spectrodensitometer X-Rite 504.
<Contrast>
The contrast, which is the difference between the whiteness and the blackness after erasing, was calculated.
その結果を表１に示す。 The results are shown in Table 1.
ハードフェライト粒子を使用していないものは表面からの消去性が劣る結果であり、ハードフェライト粒子と組み合わせるマグネタイトの粒径が大きいと黒色度、コントラストが劣り、実施例１が優れた結果であった。 Those without hard ferrite particles were inferior in erasability from the surface, and when the particle size of magnetite combined with the hard ferrite particles was large, the blackness and contrast were inferior, and Example 1 was an excellent result. ..
本発明は、消去性、コントラストの優れた記録表面側から消去可能なマイクロカプセル磁気泳動ディスプレーとして文具、玩具などとして幅広く利用される。
The present invention is widely used as a stationery, a toy, etc. as a microcapsule magnetic electrophoresis display that can be erased from the recording surface side having excellent erasability and contrast.
Claims (3)
（１）油性分散媒が引火点７０℃以上であり、１５℃における体積密度が０．７５〜０．９１ｇ／ｃｍ3 であり、４０℃における動粘度が７ｍｍ2 ／ｓ以下である一種または数種の混合油状液体である。
（２）上記（１）の油性分散媒には、ＨＬＢ値が５．０以下の常温下で液状である非イオン界面活性剤を０．５〜８．０重量％を含有せしめたものである。
（３）前記分散液の画像形成素子分散後の体積密度が、画像形成素子である光吸収性磁性体と光反射性非磁性体の双方の混合粒子を用いて１．０〜１．２ｇ／ｃｍ3 に調整されたものである。 The microcapsule magnetic electrophoresis display that can be erased from the recording surface side according to claim 1, wherein the dispersion liquid encapsulated in the microcapsules has the following properties and characteristics.
(1) A type or number of oil-based dispersion medium having a flash point of 70 ° C. or higher, a volume density of 0.75 to 0.91 g / cm 3 at 15 ° C., and a kinematic viscosity of 7 mm 2 / s or lower at 40 ° C. It is a mixed oily liquid of seeds.
(2) The oily dispersion medium of (1) above contains 0.5 to 8.0% by weight of a nonionic surfactant which is liquid at room temperature with an HLB value of 5.0 or less. ..
(3) The volume density of the dispersion liquid after dispersion in the image-forming element is 1.0 to 1.2 g / g using mixed particles of both a light-absorbing magnetic material and a light-reflecting non-magnetic material, which are image-forming elements. It was adjusted to cm 3 .
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| JP2850056B2 (en) * | 1990-12-28 | 1999-01-27 | 株式会社 日本カプセルプロダクツ | Magnetic display system |
| JPH0854841A (en) * | 1994-08-10 | 1996-02-27 | Chemitec Kk | Microcapsule for magnetic display |
| JPH1176801A (en) * | 1997-07-16 | 1999-03-23 | Matsumoto Yushi Seiyaku Co Ltd | Micro capsule containing magnetic body and use thereof |
| JP2002166659A (en) * | 2000-12-01 | 2002-06-11 | Minolta Co Ltd | Rewritable recording medium |
| JP4089808B2 (en) * | 2001-12-25 | 2008-05-28 | ケミテック株式会社 | Erasable microcapsule magnetophoretic display sheet |
| JP3964373B2 (en) * | 2003-09-24 | 2007-08-22 | ケミテック株式会社 | Microcapsule magnetic recording sheet for facsimile transmission |
| JP5294715B2 (en) * | 2008-06-09 | 2013-09-18 | 株式会社日本カプセルプロダクツ | Microcapsule magnetophoretic display |
| CN101481241A (en) * | 2008-12-24 | 2009-07-15 | 海宁市凌通电子有限责任公司 | Preparation of complex phase nanocrystalline permanent ferrite material |
| JP5971527B2 (en) * | 2013-05-25 | 2016-08-17 | コニカミノルタ株式会社 | Magnetophoretic display |
| US10444553B2 (en) * | 2014-03-25 | 2019-10-15 | E Ink California, Llc | Magnetophoretic display assembly and driving scheme |
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