TW526347B - Thin microcapsule magnetic flowing display plate and its using method - Google Patents

Abstract

A thin micro capsule magnetic migration display sheet is disclosed, which comprises micro capsules with an average grain size of 30-170 μm, a solid dispersion layer with a thickness of 50-360 μm, and the whole thickness of the micro capsule magnetic migration display sheet is not more than 700 μm. In addition, a protective member of 10-200 μm is provided on this. The solid dispersion layer is coated with an ultraviolet curing resin. Magnet is used to proceed recording and erasing on the display sheet. The display sheet is light, thin, and small, in which the contrast difference of white and black is high, recorded characters are clear, and the erasing is performed clearly.

Description

526347 _Case No. 89113340_ Revised Year of the Month _ V. Description of the Invention (1) [Field of the Invention] The present invention relates to a thin microcapsule magnetic swimming recording board. More specifically, the present invention relates to a thin, light and short card for information display or recording. A thin microcapsule magnetic swimming recording board which can be used from the surface side for recording to erasing, and a method of using the same. [Background of the Invention]

A known magnetic display panel and magnetic recording method are microcapsule coatings formed by coating microcapsules on a non-magnetic substrate with a light-absorptive magnetic powder and a light-reflecting non-magnetic fine powder (white) on the inside. Layer, further provided with a structure of a transparent protective layer to prevent the microcapsules from being damaged due to friction pressure, and slides in the magnetic device from one end to the other end of the display inside the structure, so that the magnetic powder in the microcapsules moves downward At the same time, the non-magnetic powder is moved to the upper part to make the display white, and then the surface side is moved with a rod-shaped permanent magnet to move the magnetic powder upward to display characters and the like (for example, JP 2-1 4 6 0 8 2). In addition, the use of a microcapsule magnetic display panel having a particle diameter in the range of 200 to 6 0 // m is disclosed, and it is also disclosed to be used in a toddler's drawing book, a toddler's toy, a memo board, or a meeting blackboard. In addition, in recent years, it has been disclosed that credit cards, prepaid cards, and the like have been popularized. As a POP (Particle Oriented Paper), a microcapsule magnetic recording board containing dispersed magnetic powder has been cut to a specific size. Various cash with mechanically readable magnetic recording surface

Page 4 526347 _Case No. 89Π3340_ Year Month Revision __ V. Description of the Invention (2) ^ Withdrawal cards, credit cards, prepaid cards, time coupons and other cards (hereinafter referred to as cards) are used. (See Japanese Patent Application Laid-Open No. 5- 1 6 5 79 and Japanese Patent Publication No. 7-70 0 39.) [Problems to be Solved by the Invention] β However, a part of the card surface with a thickness of about 7 6 0 // m is cut out to a thickness of about 2 7 5 // m to form a groove, and the aforementioned microcapsule magnetism is embedded in the groove. When using a recording board (also called a microcapsule magnetic display board), since the particle size of the microcapsule is 2 0 ~ 6 0 0 // m, the thickness of the card made with it is 1 0 0 0 // m φ or more. Only the microcapsule magnetic display board partially protrudes, which will cause obstacles during use. In addition, if the card is made of a thickness as a raw material, the aforementioned obstacles can be covered, but in terms of lightness, shortness, and shortness, it is not satisfactory. product. Therefore, the present inventors have considered the combination with a card to form a thin microcapsule magnetic recording plate as much as possible, and have conducted various researches on this subject. It has been found that when the microcapsules are made small to form a thin magnetic recording plate, the characters The contrast is extremely low, so there will be a problem that it will not function as a recording plate. If the ratio of magnetic particles and white pigment contained in the microcapsules and the type of dispersant are changed, a record printing with excellent contrast can be obtained. Eliminate from the same side (printed side). Based on this finding, the present invention is completed. Therefore, the first problem to be solved by the present invention relates to lightness, thinness, and shortness. From recording to erasing, it can be performed on the same side. It can record sharp characters regardless of the type of note magnet or erasing magnet. In addition, it can be cleaned and erased. It is easy to see the thin black and white contrasts. Microcapsule magnetic

526347 _Case No. 89113340_Year Month Day__ V. Description of the invention (3) Sexual recording board and its using method. In addition, the second problem to be solved by the present invention relates to a thin microcapsule magnetic recording board suitable for use in a card, etc., which can be performed on the same side from recording to erasing, and a method of using the same. [Means for solving the problems of the present invention] The above-mentioned problems of the present invention can be achieved by the inventions described in the following patent applications. (No. 1 in the scope of patent application) · A thin microcapsule magnetic swimming display plate, which is characterized in that it is mixed with a binder and contains microcapsules with a dispersion liquid, white pigment, microparticle thickener and magnetic particles inside. In a microcapsule magnetic swimming display panel formed by a solid dispersion layer formed on one side of a support body, (1) the average particle size of the microcapsules is 30 to 1 7 0 // m; (2) the thickness of the solid dispersion layer is 50 ~ 360 // m; (3) The total thickness of the microcapsule magnetic swimming display panel is 7 0 0 // m or less. (Item 2 of the scope of patent application) The thin microcapsule magnetic swimming display panel described in item 1 of the scope of patent application, characterized in that the support is formed of a transparent plate of 10 to 100 m //. (Item 3 of the scope of patent application) The thin microcapsule magnetic swimming display panel as described in item 1 or 2 of the scope of patent application, characterized in that

526347 _Case No. 89113340_Year Month and Date__ V. Description of the invention (4) The surface of the scattered layer has a protective layer of 10 ~ 200 // m. (Patent application scope item 4) The thin microcapsule magnetic swimming display panel according to item 1 of the patent application scope, characterized in that the support is a peelable layer, and the peelable layer is peeled and removed to become unsupported. A thin microcapsule magnetic swimming display panel formed of only a solid dispersion layer. (Item 5 of the scope of patent application) The thin microcapsule magnetic swimming display panel according to any one of the scope of claims 1 to 4, wherein the solvent in the dispersion liquid is selected from the group consisting of At least one or more low boiling point solvents of xylene, xylene, ethylbenzene, methylcyclohexane, ethylcyclohexane and cyclohexane, and selected from dodecylbenzene, dipentylbenzene, diphenyl ether At least one of the high-boiling solvents of dibenzoyl benzoate or phenylxylylethane, diethylbenzene, pentylbenzene, ethyl phthalate, and butyl furoate is formed, and their ratio is For 100 parts by weight of a low boiling point solvent, high boiling point solvents are 20 to 250 parts by weight. (Item 6 of the scope of patent application) The thin microcapsule magnetic swimming display panel according to any one of the scope of claims 1 to 5, wherein the white pigment has the same particle diameter as the magnetic particles White pigment. (Item 7 of the scope of patent application) The thin microcapsule magnetic swimming display panel according to any one of the scope of claims 1 to 6, wherein the ratio of the magnetic particles to the dispersion is (K 3〜1 0. 0 重量 ％, the ratio of titanium oxide is 5. 0 ~ 5 0. 0%, In addition, for magnetic particles, titanium oxide's

526347 _Case No. 89113340_ Year Month Revision _ 5. Explanation of the invention (5) The ratio is 4 ~ 30. (Item 8 of the scope of patent application) The thin microcapsule magnetic swimming display panel according to any one of the scope of claims 1 to 7 of the scope of patent application, characterized in that at least one of the aforementioned binder or the solvent of the dispersion liquid A colorant that is dispersed or dissolved. (Item 9 of the scope of patent application) The thin microcapsule magnetic swimming display panel as described in any one of the scope of claims 1 to 8 of the scope of patent application, characterized in that it is recorded with a magnet on the surface and from the surface eliminate. (Article 10 of the scope of patent application) · Pen-type note magnets, characterized in that the diameter is 0.3 ~ 2.0 mm, and the surface magnetic flux density is above 700 Gauss. (Article 11 of the scope of patent application)-A magnet for elimination, which is formed of an isotropic or anisotropic titanium hafnium magnet with a surface magnetic flux density of 100 to 750 Gauss. (Item 12 of the scope of patent application)-Elimination magnets are characterized by using rare-earth cobalt magnets or rare-earth iron magnets and placing them at a distance of 5 mm to 40 mm from the surface. Since the thin microcapsule magnetic swimming recording plate of the present invention described in item 1 of the scope of the patent application, (1) the average particle diameter of the microcapsules is 30 to 1 7 0 // m; (2) the thickness of the solid dispersion layer is 5 0 ~ 3 6 0 // m; (3) Micro glue

526347 _Case No. 89113340_ Year and month amendment_ V. Description of the invention (6) The total thickness of the capsule magnetic swimming display board is less than 7 0 0 // m, thin and short, and notes and elimination can be performed on the same side, regardless of the use of notes Any type of magnet or erasing magnet can record bright characters, etc., and it can be erased cleanly. It is easy to see notes with sharp contrast in black and white. It is an excellent product. In the present invention described in item 2 of the scope of patent application, since the support body is formed of a transparent plate of 10 to 1 0 // in, it can be used as various cash withdrawal cards, credit cards, prepaid cards, time coupons, etc. use. In addition, the invention described in item 3 of the patent application, the surface of the solid dispersion layer has a protective layer of 10 to 2 0 // m, which can completely protect the solid dispersion layer containing microcapsules. In addition, in the present invention described in item 4 of the scope of patent application, since the support is a peelable layer, the thin microcapsule display panel formed of only a solid dispersion layer without the support after peeling off the peelable layer, therefore, not only It can be used as a magnetic pen for writing, and can be a thin microcapsule magnetic swimming display board with a mechanically readable magnetic recording surface. In the present invention described in claim 5, the solvent in the dispersion liquid is at least one selected from the group consisting of toluene, xylene, ethylbenzene, methylcyclohexane, ethylcyclohexane, and cyclohexane. More than one low boiling point solvent and selected from the group consisting of dodecylbenzene, dipentylbenzene, diphenyl ether, dibenzoate, phenylxylylethane, diethylbenzene, pentylbenzene, phthalate At least one or more high boiling point solvents of ethyl formate and butyl furoate are formed, and their ratios are 20 to 250 parts by weight for 100 parts by weight of low boiling point solvents and high boiling point solvents. The dispersoid is adjusted to maintain the dispersed state. In the invention described in claim 6, the white pigment is a white pigment having the same particle diameter as the magnetic particles. Therefore, not only the magnetic particles are excellent in mobility, but also sharp contrast characters and day images can be obtained.

526347 _ Case number 89Π3340_ 年月 日 __ V. Description of the invention (7) In addition, the scope of application for the seventh item of the patent, because for the dispersion, the ratio of magnetic particles is 0.3 to 1 0. 0% by weight, titanium oxide The ratio is 5.0 to 5 0.0%. In addition, the ratio of titanium oxide to magnetic particles is 4 to 30. Therefore, a clear image with excellent contrast can be obtained even with a thin type. In the invention described in claim 8 of the application, since a colorant is dispersed or dissolved in at least one of the aforementioned binder or dispersion solvent, the surface or the back surface of the recording board can be colored to a desired color. In the invention described in claim 9 of the scope of patent application, since a magnet is recorded on the surface and eliminated from the surface, a thin capsule magnetic swimming recording plate can be used. In the invention described in item 10 of the scope of patent application, since a magnet having a characteristic value of 0.3 to 2.0 mm in diameter and a surface magnetic flux density of 700 Gauss or more is used, a microcapsule magnetic swimming recording plate with better contrast can be obtained. In the invention described in item 11 of the scope of the patent application, since it is formed of an isotropic or anisotropic titanium hafnium magnet having a surface magnetic flux density of 100 to 750 Gauss, a microcapsule magnetism with better contrast can be obtained. Record board. In the invention described in item 12 of the scope of the patent application, since the rare earth magnet or the rare earth iron magnet is used for elimination, and it is placed and used at intervals of 5 mm to 40 mm from the surface, it can be more uniform and clean. Perform elimination. [Mode for Carrying Out the Invention] Embodiments of the present invention will be described below. This is only an example, and the present invention is not limited thereto. The thin microcapsule magnetic swimming recording plate of the present invention is a microcapsule mixture in which a dispersion liquid and magnetic particles are enclosed in an interior mixed with an adhesive.

526347 _Case No. 89113340_Revision of the month and month_ 5. Description of the invention (8) A solid dispersion layer (so-called microcapsule dry coating layer) is formed on one side of the support, and a microcapsule magnetic swimming recording plate formed by the solid dispersion layer (1) the average particle size of the microcapsules is 30 ~ 1 7 0 // m; (2) the thickness of the solid dispersion layer is 50 ~ 3 6 0 // m; (3) the microcapsule magnetic swimming display panel A thin microcapsule magnetic swimming display panel characterized by a total thickness of 7 0 0 // m or less. In this configuration, the solvent is a solvent in which a low-boiling solvent and a high-boiling solvent are combined as a dispersant.

In the present invention, the solvent in the dispersion liquid is substantially insoluble in water, and is a solvent which is stable during the microencapsulation process and has compatibility between the solvents. In addition, in order to allow magnetic materials (such as magnetic particles) to move well and provide good contrast, it is preferable to use a low-boiling solvent in combination with a high-boiling solvent. Examples of the low-boiling solvents include toluene, xylene, ethylbenzene, methylcyclohexane, ethylcyclohexane, and cyclohexane. These low boiling point solvents can be used alone or in combination of two or more.

The high boiling point solvents that can be used in the present invention are dodecylbenzene, dipentylbenzene, diphenyl ether, benzyl benzoate, ethyl phthalate, phenylxylylethane, diethyl Benzylbenzene, amylbenzene, ethyl phthalate and butyl furoate. These high-boiling-point solvents can be used individually or in mixture of 2 or more types. In addition, the mixing ratio of the low-boiling point solvent and the high-boiling point solvent is 20 to 250 parts by weight with respect to 100 parts by weight of the low-boiling point solvent, and preferably 100 parts by weight of the low-boiling point solvent. The high boiling point solvent is 30 to 150 parts by weight, and more preferably the high boiling point solvent is 40 to 100 parts by weight relative to 100 parts by weight of the low boiling point solvent. When the addition ratio of the high-boiling solvent is less than 20% by weight relative to the low-boiling solvent, the dispersion of the low-boiling solvent cannot be prevented. In addition, in order to disperse the magnetic material and the white pigment in a solvent, a ball must be used.

Page 11 526347 _Case No. 89113340 _ Years and Months Amendment _ V. Description of the Invention (9) Mills and other materials are mixed. Since it is not possible to use only low-boiling solvents with high volatility in the mixing, more than 20% by weight must be used. High boiling point solvents are mixed. When the high-boiling-point solvent exceeds 250% by weight, the mobility of the magnetic particles is deteriorated.

In the present invention, the average particle size of the microcapsules described in the above (1) is 30 to 170 // m, preferably 40 to 150 // m, and more preferably 50 to 130 // m. In the present invention, since the average particle diameter is in a range of 30 to 17 0 // m, it is possible to record sharp characters and the like regardless of the type of the magnet for writing or the magnet for erasing, and to eliminate it cleanly, which is not only easy to see Black and white contrast notes, and can be made into a thin microcapsule magnetic recording board. The thickness of the solid dispersion layer described in the above (2) is 50 to 3 6 0 // m 5, preferably 50 to 300 // ΙΠ, and more preferably 60 to 250 // m. If the thickness is less than 5 0 // m, the contrast of the displayed image becomes very unclear, and if it exceeds 360 // ΙΠ, it may cause obstacles in the use as a thin type, so it is not preferable. In addition, in the present invention, the total thickness of the microcapsule magnetic swimming display panel is less than 7 0 // // m. If it exceeds this thickness, it cannot be used for thin applications. In addition, this lower limit is substantially the same as the thickness of the solid dispersion layer.

In the thin microcapsule magnetic swimming recording plate of the present invention, the thickness of the support (surface plate) is 10 to 100 mm. The support may be transparent or opaque, but when viewed directly, a transparent substance is used. As such a transparent plate, polyester films such as polyethylene terephthalate, polyethylene film, polypropylene film, vinyl chloride film, and polycarbonate film can be preferably used. It is not limited to these, and a polyethylene terephthalate film is preferable.

Page 12 526347 _Case No. 89113340_ Year Month Amendment _ V. Description of Invention (10)

In the present invention, a protective layer of 1 to 2 0 0 // m may be provided inside the solid dispersion layer (on the surface side opposite to the support). Specifically, the aforementioned polyester resin may be used for these protective layers. For example, transparent or non-transparent resins such as polyethylene terephthalate, polyethylene resin, polypropylene resin, vaporized ethylene resin, polycarbonate resin, ultraviolet curable resin, etc. Adhesive or adhesive bonding. It may be bonded to paper, aluminum foil, rubber layer, etc. other than these films. In terms of manufacturing efficiency, resin coating and drying are preferred. The effect of the protective layer is to relieve the local pressure on the microcapsules, thereby preventing the destruction of the microcapsules. Relieving the local pressure on the microcapsules means that the transparent film layer will not sag, will not be damaged, and will not damage its flexibility compared to the pressure on the note. Therefore, the hardness of the transparent film layer can be adjusted according to the method of adjusting the resin hardness of the transparent film and the thickness of the product to be used which is specified by the resin hardness of the transparent film layer.

In the present invention, when a thin film (or sheet) as a protective layer is provided on the surface of the solid dispersion layer, the film is preferably adhered with a bonding agent (herein, the term bonding agent includes an adhesive). The adhesive used here is not particularly limited, and a wide variety of adhesives and adhesives can be used. For example, in natural rubber, polyurethane resin, acrylic resin, isoprene rubber, styrene butadiene rubber, styrene butadiene block copolymer, styrene isoprene block copolymer, butyl rubber, Polyisobutylene, silicone rubber, polyvinyl isobutyl ether, gas butadiene rubber, nitrile rubber, graft rubber, recycled rubber and other elastomers are added with bonding agents, softeners, anti-aging agents, fillers, etc. Production. Natural rubber, styrene butadiene, polyisoprene, acrylic, silicone rubber, etc.

Page 13 526347 Case No. 89113340 Amendment V. Description of Invention (11) Agent. Since the adhesive layer is provided in this manner, the microcapsule can be sufficiently protected.

The thickness of the adhesive layer, while protecting the microcapsules, is not too thick in terms of eliminating the relationship between the recorded record and goodness. Of course, it should not be too thick under the restrictions of the so-called thin plate. Therefore, the thickness of the bonding layer is preferably 1 0 to 1 8 0 // m. More preferably, it is 3 0 to 1 3 0 // m. This adhesive layer not only joins the film and the solid dispersion layer, but also prevents the microcapsules in the microcapsule coating layer from being damaged by the pressure in the note, so it can display bright text or portraits for a long time, and make the microcapsule magnetic display board It becomes a product with excellent durability. That is, when the thickness of the bonding layer is thinner than 10 m, the protection of the microcapsules is insufficient, and the microcapsules may be damaged due to the pressure in the pen record. In addition, when the thickness exceeds 1 0 0 // m, although sufficient protection can be obtained, it is not good to use a reverse magnet to eliminate recording from the recording surface side, which is not good. In addition, as a magnet for elimination, it is necessary to use a strong Magnets are not economical.

In the present invention, it is more preferable to use an ultraviolet curable resin adhesive as the protective layer. That is, the solid dispersion layer is coated with an ultraviolet curable resin, and then a thin transparent synthetic resin film is bonded to the solid dispersion layer and irradiated with ultraviolet rays to harden it, or the solid dispersion layer is coated with an ultraviolet curable resin, and the A method of bonding a thin transparent synthetic resin film to the substrate and curing it by irradiation with ultraviolet rays. The bonding agent in the bonding layer is preferably a bonding agent or a bonding method which can be closely bonded to the surface of the solid dispersion layer having fine unevenness and does not form voids. Therefore, in this regard, for example, the microcapsule coating layer is preferably used. A method of applying a UV-curable resin to a bonding agent layer. Because the solid dispersion layer and the adhesive layer are fully and tightly joined (integrated)

Page 14 526347 _Case No. 89113340_ Year and month amendment_ V. Description of the invention (12)), therefore, not only can improve the flexibility (strength against bending) of the microcapsule magnetic display panel, but also fully protect the micro capsule.

In addition, when the ultraviolet curable resin is used, specifically, when coating on a solid dispersion layer, a liquid ultraviolet curable resin can be directly applied, and the liquid ultraviolet curable resin is cured by irradiation with ultraviolet rays to form a protective layer. Alternatively, a UV-curable resin is used for the solid dispersion layer. When the film is bonded, a liquid UV-curable resin is coated on the solid dispersion layer, and a synthetic resin film is loaded on the solid-dispersion layer, and the liquid UV-curable resin is irradiated with ultraviolet rays. Hardened, solid dispersion layer is integrated with UV-curable resin. Therefore, the synthetic resin film may be peelable if necessary.

In the present invention, the support is a peelable layer, and the peelable layer is characterized by being formed of only a solid dispersion layer after peeling. Since the peelable layer is peeled after the solid dispersion layer is formed, its thickness is not particularly limited, and an appropriate thickness within a range in which the solid dispersion layer can be formed satisfactorily can be selected. As the peelable layer, a release agent-coated support is usually used, and a support which is not bonded to the solid dispersion layer is particularly preferred. For example, when polyvinyl alcohol is used as a bulking agent for the solid dispersion layer and a polyethylene terephthalate film is used as a support, there is no adhesion between the two, and it can be easily peeled off after coating and drying. In addition, as the release agent, it is preferable to use Shibaishi oil and F resin oil. The dispersion liquid in the microcapsule used in the present invention contains at least one kind of magnetic particles, non-magnetic particles, and the like, and it is preferable that the particle sizes of the magnetic particles and the non-magnetic particles are the same. In addition, a dispersant is used here, and it is preferable to further disperse using a mechanical method such as a ball mill. This allows magnetic or non-magnetic particles

Page 15 526347 Case No. 89113340 Rev. V. Description of the Invention (13) Dispersions such as particles are dispersed uniformly and for a short time. In addition, it is also preferable to include a fine particle thickener in the dispersion liquid, so that it has the effect of preventing the more uniformly dispersed dispersant from being precipitated and maintaining a stable state for a long time.

In the present invention, examples of the dispersant for dispersing magnetic particles include polyethylene oxide lauryl ether, polyethylene oxide cetyl ether, polyethylene oxide stearyl ether, and polycyclohexyl ether. Ethyl oleyl ether, anionic aliphatic ester mixture, polycarboxylic acid amine salt, sorbitan trioleate, sorbitan monolauric acid, sorbitan monostearic acid, etc. The addition amount of the dispersant may be a usual addition amount of the dispersant, and the addition amount is 0.2% to 10% by weight, preferably 0.4% to 3.0% by weight. When the amount of the dispersant added is less than 0.2% by weight, a satisfactory dispersing effect cannot be obtained, and if it exceeds 10% by weight, the viscosity of the dispersant becomes high and the characteristics of the dispersant are impaired, so it is not preferable.

Examples of the fine particle thickener include anhydrous silicic acid, hydrous silicic acid, silicates (sodium silicate, potassium silicate, aluminum silicate, calcium silicate, etc.), alumina fine powder, silicon dioxide powder, Diatomite, kaolin, hard clay, soft clay, bentonite, ultrafine calcium carbonate, ultrafine activated calcium carbonate, bicarbonate, hydrous rhenium carbonate, barium sulfate, benzidine yellow, etc. These can be used alone or in combination of two or more. The amount of the microparticle thickener added to the dispersant may vary depending on the type of the dispersant. The amount of the microparticle thickener relative to the dispersant is 0.2% to 5% by weight, preferably 0.4% to 2% by weight. When the added amount of the microparticle thickening is less than 0.2% by weight, there is no adjustment effect on magnetic particles and non-magnetic particles, and if it exceeds 5% by weight, movement of solid particles such as magnetic particles is prevented from moving, so it is not preferable.

Page 16 526347 _Case No. 89113340 _ Years and Months Amendment _ V. Description of the Invention (14) As the magnetic particles used in the present invention, those that are commonly used in the field may be mentioned, for example, black iron oxide, Porous iron oxide, manganese dioxide-containing iron oxide, chromium dioxide, iron oxide, fine particles of iron or nickel, and magnetic particles such as iron-nickel that have not been subjected to affinity treatment, and magnetic iron oxide is particularly preferred. One kind or a mixture of two or more kinds can be used. Examples of commercially available products include Todaichi KN — 3 2 0 (ferric oxide made by Toda Kogyo Co., Ltd.), Talouskus (Xiguchi 7xa A BL — 5 0 (titanium Synthetic iron oxide manufactured by Industrial Co., Ltd.) and the like. Preferred is magnetic iron oxide represented by F e 3 0 4. The particle diameter of the magnetic particles is preferably 1 0 // m or less, and preferably 0.1 // m ~ 5 // m, more preferably 0.1 // m ~ 0.8 // m. In addition, more preferably 〇1 / 1 / ιι ~ 0.5 / zm, containing 70% or more of 0.2 // m ~ 0. 3 // m Products. If the particle diameter of the magnetic particles in the present invention exceeds 1 0 // m, the sharpness of characters and the like decreases, which is not preferable. In addition, if it is less than 0.1 // m, the speed of writing or erasing is particularly slow. 1 // m ~ 1 // m, particularly preferably 0. 5 // m ~ 1 // m. Magnetic particles subjected to affinity treatment are not preferred because they reduce the ability of the microparticle thickener. Magnetic With respect to the dispersion liquid, 0.3 to 1 0. 0% by weight, preferably 0. 5 to 7. 0% by weight, more preferably 1. 0 to 5. 0% by weight. For the dispersion, the ratio of the magnetic particles is less than 0. At 3% by weight, Vivid characters, portraits, etc. cannot be obtained. In addition, if the ratio of the magnetic particles exceeds 1.0% by weight, not only the mobility of the magnetic particles is deteriorated, but the entire particles become a little black, resulting in unsatisfactory contrast. Examples of the non-magnetic particles used in the present invention include white pigments such as titanium dioxide, barium white, zinc oxide, zinc white, and zinc sulfide.

526347 Case No. 89113340 Date of Amendment V. Description of Invention (15)

As the titanium oxide, any of anatase type and rutile type can be used. From the viewpoint of hiding power, rutile titanium oxide is preferred. These are preferably products having a small specific gravity. In addition, a product having a high oil absorption (oil absorption means that the solvent is absorbed into the particles by the particles) is preferable. The particle diameter of the non-magnetic particles is not particularly limited as long as it can be sufficiently dispersed, and is 0 · 1 // m to 1 // m, preferably 0 · 1 // in to 0. 5 // m. If the particle diameter of the magnetic particles is large and the particle diameter of the titanium oxide is small, the magnetic particles will be transported quickly, not black, and poor in contrast. In addition, if the particle diameter of the magnetic particles is small and the particle diameter of the titanium oxide is large, black appears. Although the contrast is improved, the migration of the magnetic particles becomes worse at the edges, which is not preferable. Signed by this fact, it is understood that it is necessary to make magnetic particles and non-magnetic particles exist with the same size.

The non-magnetic particles used in the present invention are 5.0 to 50.0% by weight, preferably 10.0 to 40.0% by weight, and more preferably 15.0 to 35.0% by weight for the dispersion. As for the dispersion liquid, if the ratio of the non-magnetic particles is less than 5.0% by weight, the thinness, especially the blackness of the whole, is not only poor in contrast, but also sharp characters, day images, etc. cannot be obtained. In addition, if the ratio of the non-magnetic particles exceeds 5.0% by weight, on the contrary, the whole is a little white, and satisfactory contrast cannot be obtained. From this point of view, for magnetic particles, the ratio of non-magnetic ions is 4 to 30 times, preferably 5 to 20 times, and more preferably 6 to 15 times. In this way, clear images with excellent contrast can be obtained even with a thin profile. At least one of the transparent aqueous bonding agent and the transparent film in the microcapsule coating layer or the dispersion in the microcapsule used in the present invention or the gelatin coating film of the microcapsule may contain a coloring agent for proper coloring. In this way, the back or background of the magnetic display panel can be colored in various colors. As such a colorant, a general dye or pigment can be used. As this dye or pigment,

Page 18 526347 ^ ____ Multi-number 89mg ---- ^ HB amendment ___ V. Description of the invention (16) 玎 Lists dyes such as 'methylene blue' Congo red, benzo yellow-τ z, oil cane, oil green, oil Yellow, benzylamine, etc. The microcapsules of the present invention are dispersed in an adhesive, and then coated on a substrate to form a microcapsule magnetic recording plate, and a character or day image is formed by a magnetic field. As a method for forming a character or a day image with a magnetic field on the microcapsule magnetic swimming recording plate, various methods known in the field of magnetic display layer technology can be used, and any method can be used. The mi-type microcapsule magnetic swimming display board is prepared by preparing magnetic particles containing ^ particles and dispersing, and coating the obtained dispersion on a transparent film surface sheet in. ^ ^, ΆΑ-, drying, Tong Λ, person & gt It is called < And, B is an example of a method for manufacturing a magnetic display panel using a solid dispersion layer containing microcapsules, and a detailed description of δ has included the manufacturing method. Its (1) is between 2Oc and 6O. The magnetic particles and dispersant are added to the gelatin aqueous solution, and the step of giving away the gum arabic is added; (2) The temperature of the resulting mixed solution is lowered to 20 ° C below the f 7 solution, and the pH is adjusted to make it acidic. To further form a good microcapsule; to form a polymer of gelatin / arabin gum; forming steps; (4) removing the super 3) hardening the polymer film to form the upper limit of the microcapsules, and removing the water ^ the average microcapsules obtained Large particles with a particle size adjusted for dispersion in the bonding agent, 5 2 $, (5) the step of applying the obtained microcapsules in a transparent aqueous solution to a transparent thin capsule = microcapsule dispersion; (6) drying the dispersion to form (7) a step of applying the obtained coating dispersion layer (8) on the obtained coating layer> a solid dispersion layer (coating layer) of the capsule and a step of providing a protective layer on the surface of (4). _ In the steps, in order to protect the emperor's eight sinkers, S, ra spear, and dewatering knife, the aqueous solution was passed. 526347 _ Case No. 89113340

Concentrate to 40% ~ 70% to form a microcapsule coating with appropriate viscosity. In the step (5), the water-based transparent bonding agent may be any one of a water-based polyurethane resin, a water-based aromatic polyester resin, or a water-dispersed polyurethane resin, and together with the protective layer, it can be manufactured into a thin micro-durable resin with excellent durability. Capsule magnetic swimming display board. In addition, the viscosity of the microcapsule dispersion is preferably an appropriate viscosity for the support (substrate) coating. The viscosity can be changed according to the temperature of the four seasons or various coating conditions. Generally, the viscosity is adjusted to 1, 0 0 0 cps ~ 2 After 0,0 0 0 cps, the viscosity-adjusted dispersion is coated on a substrate, and a microcapsule coating layer is formed after drying, so that more vivid characters or day images can be recorded. In addition, as described in the step (8) above, by bonding a sheet layer containing a bonding agent layer to the surface of the solid dispersion layer (coating layer), voids (air bubbles) can be formed in the surface irregularities of the microcapsule coating layer. Add a bonding agent in the place to get a close joint. In addition, in the step (8), when the pressure buffer layer is any of a plastic film or a hard or soft film, it can be used in combination with a device that uses a light source to illuminate from the back to produce a microcapsule magnetic display panel.

In addition, the method of coating the microcapsules on the substrate may be performed by a general coating method such as a bristle coating method, a screen printing method, an air curtain method, or a dip coating method. After drying, the drying temperature may be a range commonly used in the art, for example, 40 ° C ~ 120 ° C, preferably 50 ° C ~ 9 (TC. In addition, the drying time is usually preferably 10 minutes ~ 2 Hours, more preferably 30 minutes to 50 minutes. In addition, as the drying method, hot air drying or convection drying is preferred. The microcapsule magnetic swimming display panel of the present invention is on the surface of the plate,

Page 20 526347 _Case No. 89113340_Year Month Amendment _ V. Description of the invention (18) After the text or image formed on the surface is completely removed by moving the erasing magnet, use a pen-type note magnet to write text or image on the surface. Day painting can get a vivid record. The record drawn in this way is erased by the erasing magnet. In addition, according to the microcapsule magnetic swimming display panel of the present invention, a writing magnet or a picture on the surface can be removed by a conventional method on the back side of the board. Then, a writing pen can be used on the surface to write characters and pictures. painting.

In the microcapsule magnetic display panel of the present invention, when using a magnet for recording or erasing, it is preferred to use a pen-type note magnet with a diameter of 0. 3 to 2 mm and a characteristic value of a magnetic flux density of 7 0 Gauss or higher, preferably a rare earth The magnet-like magnet is preferably a magnetized IP (magnetism of 700 gauss or more under such conditions). Covering the magnet, especially the top end of the magnet with a ferromagnetic material, can concentrate the magnetic force distribution and obtain an effective sharp record. When the diameter of the magnet is less than 0.3 mm, the microcapsules may be damaged or the surface panel may be damaged, and it may be dangerous to use. If the diameter of the magnet exceeds 2.0 mm, the magnetic force distribution becomes wider, and the sharpness of the note is not good.

When erasing a recorded character or the like, it is preferable to use an erasing magnet having a surface magnetic flux density of 100 to 75 Gaussian characteristic value. The magnet used here can be changed according to the use of the surface plate, and can be widely used according to its use. There is no particular limitation on this. It can be any shape such as cylindrical, coin-shaped, rod-shaped, or angular-pillar. Choose the appropriate size. The magnets used are preferably rare earth magnets such as iron-coated oxygen magnets, rare earth magnets (for example, samarium · cobalt magnets, etc.) or rare earth iron magnets (such as iron magnets), and bonded magnets. As the magnetization type of the magnet, it is preferable that the magnetization on both sides is I P (in this condition, it can reach 100 to 750 Gauss). Particularly preferred is the use

Page 21 526347 _Case No. 89113340 _ Year and month Amendment _ V. Description of the invention (19) Isotropic or anisotropic, rare earth magnets, ferrite magnets. If you select a magnet and magnetization type with such conditions, it can be removed cleanly. When a rare-earth magnet is used, it is more preferably placed at a distance of 2 m to 40 mm from the display surface, preferably 5 m to 20 m, to move it more cleanly.

The microcapsule magnetic display panel obtained by the manufacturing method of the present invention is thin and has excellent storage properties and convenience. In addition, although it is thin, it also has characteristics of flexibility and excellent strength, and can be used in various applications. use. For example, in addition to use in cash withdrawal cards, credit cards, access credit cards, prepaid cards, etc., for general use, there are children's toys, text trainers, various game boards, copy boards, memos, etc. Boards, conference blackboards, various information boards in clean rooms, electro-optic notice boards, computer display dashboards, etc. [Detailed description of the embodiments of the present invention] Hereinafter, the present invention will be described in more detail by means of examples. These examples are only for explaining the present invention, and the present invention is not limited to these embodiments.

Embodiment 1 FIG. 1 is a cross-sectional view of a microcapsule magnetic display panel of the present invention. In addition, the microcapsule of the present invention has a cross-sectional view shown in FIG. 2. The microcapsules 1 shown in FIG. 2 are formed by enclosing magnetic particles 3 and non-magnetic particles 4 dispersed in a dispersant 5 in a gelatin film 2. Such microcapsules are manufactured as follows. to

Page 22 526347 _Case No. 89113340 _ Year Month Day Amend _ V. Description of the invention (20)

As the magnetic particles 3, iron oxide powder particles with an average particle size of 0.3 // m (trade name Talouskus (Yu. 7々 久) BL-50, crushed by products manufactured by Titanium Industry Co., Ltd. Obtained) 2% by weight of white titanium oxide powder (trade name R — 8 2 0, manufactured by Ishihara Sangyo Co., Ltd.) with an average particle diameter of 0.2 6 6 m as non-magnetic particles 4 1 1 · 6% by weight 40% by weight of dibutyl phthalate as a high boiling point solvent and 45% by weight of toluene as a low boiling point solvent are added to the mixed solvent, and further added as a defoaming agent (Dutziber)

-SN- 3 5 0 Silicone, 0.2% by weight made by Sandubi Kob, Kogyo Co., Ltd. and micronized silicic acid as a microparticle thickener [Aerolog (7 ^^, Japan Aerolog θ Manufactured by Industrial Co., Ltd.] 0.5% by weight, and then added as a dispersant Nubicoxant 7, Koko 4 PK 9 6 3 (Sodium polycarboxylate surfactant, Sanobi Koco 7) (2) Co., Ltd.) 0.7% by weight, and dispersed.

Next, a 3.6% aqueous solution of acacia gum was added to a gelatin aqueous solution having a concentration of ρΗ6 of 3.6% to prepare an aqueous solution for a microcapsule film. The temperature was raised to about 50 ° C, and the pH of the aqueous solution was adjusted to 5 Then, the aforementioned dispersion liquid was added and stirred to make the average particle diameter of the dispersed liquid droplets approximately 100 0 // m. After the desired dispersion droplets are obtained, the temperature of the dispersion is slowly lowered and further cooled to 10 ° C. When the gelatin / arabin gum polymer film precipitates on the surface of the dispersion droplets and gels, glutaraldehyde 2 5 is added. An aqueous solution of% concentration hardens the polymer film to obtain gelatin-made microcapsules 1. Particles larger than 1 7 0 // m in the thus obtained microcapsule 1 were removed with a net, and particles smaller than 1 7 0 // m were obtained. The microcapsules have a particle size of 170 / zm or less and contain 85% of particles from 70 // m to 130 / zin. To the obtained microcapsule slurry, an aqueous polyurethane resin solution as an aqueous binder was added to the microcapsule group after removing water, and the mixture was thoroughly stirred to obtain a coating.

Page 23 526347 Case No. 89113340 Rev. V. Description of Invention (21) Ink-like product for cloth. The viscosity of this ink-like product for coating was 4,000 c ps. The obtained ink-like substance was coated on a transparent film surface sheet layer 7 having a thickness of 7 5 // m and dried with hot air at 70 ° C for 40 minutes. The thickness of the microcapsule coating layer 9 was 250 // m. Next, on the microcapsule coating layer, a 50 0 // m polyethylene terephthalate film as a protective layer 8 was further bonded with a bonding agent to prepare a microcapsule magnetic display panel. The thickness of the bonding agent layer 6 is 8 0 // m. As a result, the total thickness of the magnetic swimming display panel is 4 5 5 // m 〇

Next, a method for displaying and erasing characters on the microcapsule magnetic swimming display panel shown in Fig. 1 will be described. The surface of the transparent film surface sheet layer 7 of the microcapsule magnetic display board is contacted with a pen-type magnet for scanning. When scanning, the magnetic particles in the microcapsules swim toward the surface side. Bright black notes (note assignment). Next, by using the erasing iron-oxygen magnet contact and scanning for erasing the objects on the surface, the magnetic particles existing on the surface side of the microcapsules swim inward and near the center, and exchange and move with non-magnetic particles titanium oxide. When the surface is completely contacted and scanned with the erasing magnet, the surface becomes white, and the writing is erased (erasing operation). Here, the iron ferrite magnet for elimination mentioned above can be replaced by a rare earth magnet, and it can be removed more cleanly by scanning from a distance of 8 mm from the surface. In the present invention, although an embodiment of the microcapsule magnetic swimming display panel is described with reference to FIG. 1, the thin film membrane 8 can be peeled from the microcapsule magnetic swimming display panel to obtain a flexible in-form as a non-contact Products for sewing. In addition, as described in claim 4, a microcapsule dispersion is coated on the surface of a synthetic resin film previously coated with a release agent,

P.24 526347 _Case No. 89113340_Year Month Amendment_ V. Description of the invention (22) After drying, the synthetic resin film can be peeled off and removed, and then a film formed of only a solid dispersion layer can be used. At this time, it can be used as a board or a seamless product. [Embodiment 2] For the microcapsule magnetic display panel manufactured in Embodiment 1, the type of erasing magnet was changed, and the erasing situation was investigated. When a one-sided multi-pole magnet is used for erasing operation (moving on the surface where the text is recorded), the writing can be erased, but streaks are generated on the surface of the board and cannot be erased in a uniform state. In addition, when the erasing magnet having a surface magnetic flux density of 1100 Gauss was used for erasing, a dark surface was obtained, which cannot be said to be very good. On the other hand, in the present invention, when the erasing magnet with a surface magnetic flux density of 250 Gauss is used for erasing, it is possible to erase the notes cleanly, and to obtain a clean surface with a white surface and no unevenness. In addition, in this example, the magnet is removed by moving the magnet on the surface of the text recording. In the present invention, it goes without saying that the magnet may be removed by moving the inside of the display panel as in a conventional method. Example 3 According to the method of Example 1, (1) microcapsules having an average particle size of less than 10 // m; (2) microcapsules having an average particle size of 3 0 // m; (3) an average particle size of 1 0 0 // m microcapsules; (4) microcapsules with an average particle diameter of 1 5 0 // m microcapsules and (5) microcapsules with an average particle diameter of 2 5 0 // m, and further following the same method as in Example 1. Make a microcapsule magnetic display board and observe the state of the notes and the state of erasure. (1) other than the present invention, the entire surface is a blackened note

526347 _Case No. 89Π3340_ Year Month Amendment_ V. Description of the Invention (23) There is no comparison. In addition, the elimination state is also dark. In (5) of the present invention, since the erasure becomes slightly darker, a black-and-white pair of relatively lighter writing is formed, and there is no practical obstacle. Particularly preferred are (2) to (4) in the present invention. In each case, the elimination state is good, the color is white, the contrast with the note is large, and the effect is excellent. [Effect of the present invention]

According to the thin microcapsule magnetic swimming recording plate of the present invention, (1) the average particle diameter of the microcapsules is 30 to 17 0 // m; (2) the thickness of the solid dispersion layer is 50 to 3 6 0 // m; (3) The total thickness of the microcapsule magnetic swimming display board is less than 7 0 0 // m, so it is light, thin and short, and can be written and erased on the same side. At the same time, it can be used regardless of the type of magnet for writing or erasing magnet. Record sharp text, etc. In addition, it can be cleanly erased, and it is easy to see notes with clear white and black contrast. It is a product that can achieve these excellent effects.

In addition, in the present invention, since the support body is formed of a transparent plate of 10 to 100 m //, it can be used as various cash withdrawal cards, credit cards, prepaid cards, time coupons and other cards. In addition, in the present invention, since a protective layer of 10 to 2 μm is provided on the surface of the solid dispersion layer, the solid dispersion layer containing microcapsules can be sufficiently protected. In addition, in the present invention, since the support is a peelable layer, after peeling and removing the peelable layer, a product formed of only a solid dispersion layer without a support is obtained. Not only a pen-type note magnet but also a mechanically Thin microcapsule magnetic swimming display panel on the recording surface. In the present invention, since the solvent in the dispersion is a low boiling point solvent and a high boiling point solvent

Page 26 526347 _Case No. 89113340_Year Month Day_Charm_ V. Description of the invention (24) The point solvent is a combination of specific solvents as described above. The ratio is low boiling point relative to 100 parts by weight. The solvent and the high-boiling-point solvent are 20 to 250 parts by weight, so a good microcapsule magnetic recording plate can be obtained. In the present invention, since the colorant can be dispersed or dissolved in at least one of the solid dispersion layer or the dispersion liquid solvent, the surface or the back surface of the recording plate can be colored with a desired color.

The thin microcapsule magnetic swimming recording board of the present invention is a thin microcapsule magnetic swimming recording board which can be recorded on the surface with a magnet and eliminated from the surface. In the present invention, the magnet is a magnet having a diameter of 0.3 to 2.0 mm and a characteristic value of a surface magnetic flux density of 700 Gauss or more. Therefore, a microcapsule magnetic swimming recording plate with better contrast can be obtained. In addition, in the present invention, since the magnetic has a characteristic value of a surface magnetic flux density of 100 to 750 Gauss, a microcapsule magnetic swimming recording plate with better contrast can be obtained.

Page 27 526347 Case No. 89113340 A_ Revision Modification Brief Description [Simplified Illustration] Figure 1 is a sectional view of a microcapsule magnetic display panel of the present invention. Fig. 2 is a schematic cross-sectional view of the microcapsules for magnetic display of the present invention. [Illustration of drawing number] 1. 1 '1 2. 1 3 are microcapsules; 2. Gelatin film; 3. Magnetic particles; 4. Non-magnetic particles (Titanium oxide); 5. Dispersion liquid; 6. Protective layer (pressure buffer layer); 7. Transparent film; 8. Thin film diaphragm; 9. Solid dispersion layer (microcapsule dry coating layer 61; recessed portion).

Page 28

Claims (1)

526347 One ^ one one case number 89113340_ # · 1 Zheng Yue _ correction more _-He, Qin Zhuan spear paint ^ -One 1:-Tan thin 4 microcapsule magnetic swimming display plate, characterized in that the microcapsule magnetic swimming display plate is composed of a solid dispersion layer mixed in a binder, and the solid dispersion layer The capsule is formed on one side of the support. The microcapsule contains a dispersion liquid, a white pigment, a microparticle thickener, and magnetic particles. The dispersion liquid is composed of a combination of a low boiling point solvent and a high boiling point solvent. In the microcapsule magnetic swimming display panel, (1) the average particle diameter of the microcapsules is 30 to 1 7 0 // m; (2) the thickness of the solid dispersion layer is 50 to 3 6 0 // m; (3 ) The thickness of the solid dispersion layer and the transparent plate composed of the support body is 150 to 4 6 0 // m; (4) The thickness of the entire microcapsule magnetic swimming display panel is 5 6 0 // m or less. 2. The microcapsule magnetic swimming display panel according to item 1 of the scope of patent application, characterized in that the surface of the solid dispersion layer has a protective layer of 10 to 2 0 // // m. 3. The microcapsule magnetic swimming display panel according to item 1 of the scope of patent application, characterized in that it is composed of a solid dispersion layer without a support; the support is a peelable layer, and the peelable layer After peeling and removing, it becomes a solid dispersion layer without a support. 4. The microcapsule magnetic swimming display panel according to item 1 of the scope of the patent application, characterized in that the solvent in the dispersion is composed of a low-boiling solvent and a high-boiling solvent; wherein the former is from toluene, two At least one selected from the group consisting of toluene, ethylbenzene, methylcyclohexane, and cyclohexane starts with Page 29 526347 _ Case No. 89113340 _ Amendment _ Sixth, low boiling point solvents in the scope of patent application, the latter is from dodecylbenzene, dipentylbenzene, diphenyl ether, dibenzoyl benzoate Or at least one high boiling point solvent selected from phenylxylylethane, diethylbenzene, pentylbenzene, ethyl phthalate, and butyl furoate; the ratio of these solvents is for low boiling points The solvent is 100 parts by weight, and the high boiling point solvent is 20 to 250 parts by weight. 5. The microcapsule magnetic swimming display panel according to any one of items 1 to 4 of the scope of the patent application, wherein the white pigment is a white pigment having a particle size equal to that of the magnetic particles. 6. The microcapsule magnetic swimming display panel according to any one of claims 1 to 4, wherein the ratio of magnetic particles to the dispersion is 0.3 to 1 0 · 0. By weight%, the ratio of titanium oxide is 5.0 to 50.0 ° / 〇; Furthermore, the ratio of titanium oxide to magnetic particles is 4 to 30. 7. The microcapsule magnetic swimming display panel according to any one of claims 1 to 4, in which at least one of the binder or the solvent of the dispersion liquid has a colorant Dispersed or dissolved in it. 8. The microcapsule magnetic swimming display panel according to any one of claims 1 to 4 of the scope of patent application, characterized in that a magnet can be used to record on the surface and can be eliminated from the surface. 9. Microcapsules as described in any one of claims 1 to 4 Page 30 526347 * _Case No. 89113340_Year_Month__, VI. Patent application scope Magnetic swimming display board. The pen-type note magnet used for this display board is characterized by a diameter of 0.3 ~ 2.0mm, and The surface magnetic flux density is more than 700 ns. 10. The microgel 7-capsule magnetic swimming display panel as described in any one of the items 1 to 4 of the scope of the patent application, the elimination magnet used on the display panel is characterized by having An isotropic or anisotropic titanium hafnium magnet with a surface magnetic flux density of 100 to 750 Gauss. 11. The microgel f-capsule magnetic swimming display panel according to any one of claims 1 to 4 of the scope of application for a patent, the magnet used for the display panel for elimination is characterized by using a rare earth Cobalt magnets or rare-earth iron magnets are used at intervals of 5 mm to 40 mm from the surface. Page 31