JP4880317B2 - Reversible color change display set - Google Patents

Description

The present invention relates to a reversible color change display body set. Furthermore, the present invention relates to a reversible color-change display body set using a reversible color-change display body that can be repeatedly written and can attract a magnet.

Conventionally, a water pen paper has been disclosed as a display body capable of repeated writing due to adhesion of a liquid (see, for example, Patent Document 1).
The water brush paper can draw an arbitrary image with water or the like, and can be drawn and written repeatedly after the handwriting is dried, but has no applicability other than writing.
Japanese Utility Model Publication No. 52-44103

  The present invention provides a reversible color change display body having various usages and capable of drawing an arbitrary image with water or the like and capable of attracting magnets, and a reversible color change display body set using the same. It is something to be offered.

The present invention relates to a porous layer having different transparency in a liquid-absorbing state and a non-liquid-absorbing state, in which a low-refractive index pigment is fixed to a binder resin in a dispersed state on a magnetic support made of a plate-like magnetic body. the Ri Na provided a reversibly variable color display body porous layer side surface has a magnetic writing instrument or applicator applying plastic porous body or a fiber worked body as pen tip member having continuous pores, or the stamp member A reversible color-change display body set comprising at least one water adhering means selected from any one and a magnet is a requirement.
Further, a colored layer is interposed between the support and the porous layer, a waterproof layer is interposed between the support and the porous layer, and the waterproof layer is colored. Is a requirement.
Furthermore, it is a requirement that the water adhering means includes a magnet.

The present invention provides a reversible color change display body that can draw an arbitrary image with water or the like and can adsorb magnets by using a magnetic support for the reversible color change display body. It is possible to provide a reversible color change display body set.
Moreover, by applying various materials and forms as a support having magnetism, a reversible color change display body that can be applied to various uses such as toys and learning tools in addition to writing purposes, and reversible color change using the same. A display set can be provided.

The porous layer formed on the surface or both front and back surfaces of the support having magnetism is a layer in which a low refractive index pigment is fixed together with a binder resin in a dispersed state, and the support on the lower layer from the surface on the porous layer side. The thickness is such that the magnetism can be exhibited.
Examples of the low refractive index pigment include silicic acid and salts thereof, barite powder, barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, talc, alumina white, magnesium carbonate, and the like. It is in the range of 1.8, and when the liquid composition is absorbed, good transparency is exhibited.
Examples of the silicic acid salts include aluminum silicate, aluminum potassium silicate, sodium aluminum silicate, aluminum calcium silicate, potassium silicate, calcium silicate, calcium sodium silicate, sodium silicate, magnesium silicate, and magnesium potassium silicate.
The particle size of the low refractive index pigment is not particularly limited, but 0.03 to 10.0 μm is preferably used.
Two or more of the low refractive index pigments can be used in combination.
In addition, silicic acid is mentioned as a low refractive index pigment used suitably.
The silicic acid may be silicic acid produced by a dry process, but silicic acid produced by a wet process (hereinafter referred to as wet process silicic acid) is particularly effective and satisfies practicality.
This point will be described below.
Silicic acid is produced as amorphous amorphous silicic acid, and according to its production method, a dry process using a gas phase reaction such as thermal decomposition of silicon halide such as silicon tetrachloride (hereinafter referred to as dry process silicic acid) In general, the wet process silicic acid is the most suitable for the purpose of functioning as the porous layer intended by the present invention, although the wet process uses a liquid phase reaction such as decomposition by acid such as sodium silicate. .
This is because the dry process silicic acid and the wet process silicic acid have different structures, and the dry process silicic acid forms a three-dimensional structure in which the silicic acid is closely bound, whereas the wet process silicic acid is a long molecule formed by condensation of silicic acid. It has a so-called two-dimensional structure part that forms an array.
Therefore, since the molecular structure becomes rough compared to the dry method silicic acid, when wet method silicic acid is applied to the porous layer, it is excellent in the diffused reflection of light in the dry state compared to the system using the dry method silicic acid, Therefore, it is guessed that the concealment property in a normal state becomes large.
In addition, since the porous layer of the present invention absorbs water, the wet process silicic acid has more hydroxyl groups present as silanol groups on the particle surface than the dry process silicic acid, and has a high degree of hydrophilicity. And is preferably used.
In addition, in order to adjust the concealability in the normal state of the porous layer and the transparency in the liquid absorption state, other general-purpose low-refractive-index pigments can be used in combination with the wet method silicic acid.

The wet process silicic acid in the porous layer depends on properties such as particle size, specific surface area, oil absorption, etc., but in order to satisfy both the concealing property in the normal state and the transparency in the liquid absorbing state, it is applied. preferably the amount is ^{1g / m 2 ~30g / m 2} , more ^{preferably 5g / m 2 ~20g / m 2} . If it is less than 1 g / m ² , it is difficult to obtain sufficient concealability in a normal state, and if it exceeds 30 g / m ² , it is difficult to obtain sufficient transparency during liquid absorption.
The particle size of the silicic acid is not particularly limited, but 0.03 to 10.0 μm is preferably used.
The silicic acid is dispersed in a vehicle containing a binder resin as a binder, applied to a base material, and then the volatile matter is dried to form a porous layer.
Examples of the binder resin include urethane resin, nylon resin, vinyl acetate resin, acrylic ester resin, acrylic ester copolymer resin, acrylic polyol resin, vinyl chloride-vinyl acetate copolymer resin, maleic resin, polyester resin, styrene. Resin, styrene copolymer resin, polyethylene resin, polycarbonate resin, epoxy resin, styrene-butadiene copolymer resin, acrylonitrile-butadiene copolymer resin, methyl methacrylate-butadiene copolymer resin, butadiene resin, chloroprene resin, melamine resin, and the above Each resin emulsion, casein, starch, cellulose derivative, polyvinyl alcohol, urea resin, phenol resin and the like can be mentioned.
The mixing ratio of the silicic acid and these binder resins depends on the type and properties of silicic acid, but is preferably 0.5 to 2 parts by weight of binder resin solids, more preferably 1 part by weight of silicic acid. 0.8 to 1.5 parts by weight. When the binder resin solid content is less than 0.5 parts by weight with respect to 1 part by weight of silicic acid, it is difficult to obtain a practical film strength of the porous layer, and when it exceeds 2 parts by weight, The permeability of water into the porous layer is deteriorated.
Since the porous layer has a small mixing ratio of the binder resin to the colorant as compared with a conventionally known general coating film, it is difficult to obtain sufficient film strength. Therefore, in order to increase the scratch resistance, it is effective to use a nylon resin or a urethane resin among the binder resins.
Examples of the urethane resin include a polyester urethane resin, a polycarbonate urethane resin, and a polyether urethane resin, and two or more of them can be used in combination. In addition, a urethane emulsion resin in which the resin is emulsified and dispersed in water, or a colloid in which the resin is self-emulsified without the need for an emulsifier by an ionic group of the ionic urethane resin (urethane ionomer) itself and dissolved or dispersed in water. A dispersion type (ionomer type) urethane resin can also be used.
The urethane-based resin may be either an aqueous urethane-based resin or an oil-based urethane-based resin, but in the present invention, an aqueous urethane-based resin, in particular, a urethane-based emulsion resin or a colloidally dispersed urethane-based resin is suitable. Used for.
The urethane resin can be used alone, but other binder resins can be used in combination depending on the type of support and the performance required for the coating. When a binder resin other than the urethane resin is used in combination, in order to obtain a practical film strength, it is preferable to contain 30% or more of the urethane resin in a solid content weight ratio in the binder resin of the porous layer.
In the binder resin, the crosslinkable resin can be further improved in film strength by adding an arbitrary crosslinking agent and crosslinking.
The binder resin has a large or small affinity with water. By combining these, the penetration time into the porous layer, the degree of penetration, and the slow speed of drying after the penetration can be adjusted. Furthermore, the said adjustment can be controlled by adding a dispersing agent and surfactant suitably.

In the porous layer, conventionally known titanium dioxide-coated mica, iron oxide-titanium dioxide-coated mica, iron oxide-coated mica, guanine, sericite, basic lead carbonate, acidic lead arsenate, bismuth oxychloride, etc. The color change can be diversified by adding a metallic luster pigment or mixing general dyes and pigments, fluorescent dyes and fluorescent pigments.
In addition, conventionally known reversible thermochromic pigments that reversibly change color according to temperature change can be mixed, and the color can be changed depending on the environmental temperature or the water temperature to be adhered.
Furthermore, the color change can be further diversified by providing a colored layer in the upper layer, the lower layer, and / or the vicinity of the porous layer.
The porous layer and the colored layer are not limited to solid prints, and may be images (colored images) of characters, symbols, designs, and the like.
The porous layer and the colored layer are conventionally known means, for example, printing means such as screen printing, offset printing, gravure printing, coater, tampo printing, transfer, brush coating, spray coating, electrostatic coating, electrodeposition coating. It can be formed by flow coating, roller coating, dip coating or the like.

  In particular, when forming a colored image on a porous layer, it is an element as a learning material that allows you to trace and enter time by forming hiragana and alphabet letters with letters, or forming an external appearance of a clock Can be given in addition to the decorating effect, making it more useful.

  As the support having magnetism, a general-purpose magnetic material can be used as long as it can adsorb a magnet. Specific examples include iron, cobalt, nickel, magnetite, manganese ferrite, nickel ferrite, cobalt ferrite, barium ferrite, nickel zinc ferrite, copper zinc ferrite, manganese zinc ferrite, magnesium zinc ferrite, tungsten, etc. You can also use it. The magnetic material is used in at least one kind, and can be used even in a magnetized state (so-called magnet). When a magnetized material is used, the display body (support body) can be used by being attracted to a substrate made of another magnetic material. Furthermore, in the display body in which the surface of the porous layer has magnetism, when a magnetized one is used, other magnetic bodies (steel paper, metal pieces, etc.) can be attached to the surface of the porous layer. It becomes more highly applicable.

  As the support, in addition to directly using the above-mentioned magnetic material in a plate shape (including a foil shape), a powdered magnetic material is dispersed in rubbers or other resin compositions to form a sheet, plate or solid. It can be applied as a molded article such as a product.

In addition, as the support, the magnetic layer may be formed by applying the plate-like (foil-like) magnetic substance to an arbitrary base material, or applying and adhering a coating liquid or sheet that disperses the powder-like magnetic substance. What was provided can also be used.
At that time, by using a flexible material such as a woven fabric, a knitted fabric, a braided fabric, a non-woven fabric, a paper, a plastic film or the like as the base material, both the front and back surfaces of the support are used. Since magnetism can be imparted and folding and rounding are possible, it is possible to improve the capacity. Furthermore, since it has a softness | flexibility, it becomes the thing excellent in the safety | security at the time of an infant drawing. Further, since the substrate area can be easily formed in a large area of 2000 cm ² or more, it is useful for writing toys, wallpaper, and the like.
In addition, by using a three-dimensional object such as wood, earthenware, or resin molded product, the texture and decorativeness of the obtained display body can be improved.

  Moreover, it can also interpose as a waterproof layer which consists of a non-water-permeable film and an adhesive agent between the said support body and porous layer. Thereby, since it can suppress that a liquid penetrate | invades into the lower layer of a porous layer, even if it is a case where the support body which is easy to rust is used, corrosion of a support body can be suppressed. The waterproof layer is not limited to a transparent layer, and a colored layer can also be used. Moreover, it is also possible to provide the said waterproof layer on the back surface of a support body.

  Furthermore, a colored layer can be interposed between the layers. This makes it possible to diversify the color tone visually recognized when the porous layer is in a liquid-absorbing state, and it is easy to form a colored layer having a design or a pattern, thereby increasing the added value.

The shape of the support is not particularly limited, and is preferably a shape imitating a polygon such as a square, a rectangle, a triangle, a hexagon, a circle, an ellipse, a bowl, and other shapes such as animals, plants, and vehicles. A plate-like object or a three-dimensional object can be used. In particular, when a polygon is used, it is preferable to chamfer the acute angle portion of the apex or form a curved surface in order to further increase safety.
In addition, the support may be provided with a gripping portion in order to improve carrying performance.

As a method of adhering water to the reversible color change display body, a method of wetting hands and fingers with water and contacting the porous layer, a writing or applicator having a brush tip or a fiber pen body at the tip, or A method of impregnating water into a sponge and bringing it into contact with the porous layer, a method of bringing a container containing water close to or in contact with the porous layer, and attaching water by deriving it from the inside of the container, and open cells or closed cells on the marking surface A method for impregnating water with a stamping tool having a foam adhered thereto and adhering it to a porous layer, a method for adhering water to a stamping tool with a rough marking surface of plastic or rubber, and bringing it into contact with the porous layer It is done.
In addition, as a method for bringing a container containing water close to or in contact with the porous layer and drawing out water from the inside of the container and attaching it, the fibrous body that contains water in the container and leads out the water in the container A method of applying water with a brush, a method of containing water in a container and a method of spraying water by providing a spray device, and pressing the water in the container like a syringe to eject water Methods and the like.
Examples of the means for adhering water include a writing or applicator, a sponge, a stamp, a spray device, and a syringe. A reversible color change display set can be obtained in combination with a reversible color change display.
In addition, as a preferable water adhering means, it is a writing instrument or applicator or a stamping instrument in which a plastic porous body or fiber processed body having continuous pores is applied as a pen tip member, and an arbitrary writing image or image can be easily formed. And practicality can be improved.
The plastic porous body or fiber processed body having continuous pores in the above may be any one that absorbs and discharges water in an appropriate amount, and has been conventionally used for continuous pores and fibers of general-purpose polyolefin-based, polyurethane-based, and other various plastics. Brush-like ones in which the fibers are focused, those obtained by resin processing or heat welding of fibers, felts, and non-woven fabrics. The shape and dimensions can be arbitrarily set according to the purpose.
Further, by providing a magnet to the water adhering means such as the writing instrument, applicator, and stamp, it becomes possible to hold the magnet on the display body, so that the accommodation can be improved and the loss can be prevented.

Furthermore, by combining the display body or display body set with a magnetic material such as a stencil, a magnet, or steel paper or a metal piece, a desired image can be easily formed or adsorbed to an arbitrary portion of the display body. it can.
As the magnet, a general-purpose material such as a soft plate shape, a rod shape, or a cubic shape can be used directly, or a molded product made of resin, earthenware, glass or the like can be disposed and bonded to the above-mentioned shape.

  In the case of the reversible color change display body set, the reversible color change display body may be provided with a holding unit such as a container or a hanging hook that can hold the water adhering means. Thereby, loss of the said water adhesion means etc. can be suppressed.

Examples are shown below, but the present invention is not limited to the examples. In addition, the part in an Example shows a weight part.
Example 1 (see FIG. 1)
A red plastic film (waterproof layer 4) having a thickness of 0.1 mm is attached to the surface of the support 2 made of an iron plate having a thickness of 2 mm with an adhesive, and then wet-type silicic acid [trade name: NIPSEAL E- 200, manufactured by Nippon Silica Industry Co., Ltd.] 15 parts, urethane emulsion [trade name: Hydran HW-930, manufactured by Dainippon Ink & Chemicals, Inc., solid content 50%] 30 parts, water 50 parts, silicone-based defoaming 100 mesh screen plate using white screen printing ink in which 0.5 parts of agent, 3 parts of thickener for water-based ink, 1 part of ethylene glycol, 3 parts of blocked isocyanate-based crosslinking agent are uniformly mixed and stirred. The porous layer 3 was formed by solid printing at 130 ° C. and dried and cured at 130 ° C. for 5 minutes. Thereafter, the plate was cut into a rectangular shape having a length of 25 cm and a width of 30 cm (both top portions were formed in a curved shape) to obtain a plate-like reversible color change display body 1.
In the reversible color change display 1, the porous layer 3 having a substantially white surface is visually recognized in a dry state. However, when water is attached, the porous layer 3 changes from a white opaque state to a colorless and transparent state by liquid absorption. The color tone of the lower red plastic film is visually recognized, and the state is maintained in the liquid absorption state, but when the water is evaporated and dried, it changes to the original white state.
Further, since the reversible color changing display 1 has magnetism on the porous layer 3 side, magnets can be adsorbed on the surface of the porous layer.

Example 2 (see FIG. 2)
After arranging the decorative case 7 (comprising the accommodating part 71) which consists of a resin molding so that the outer periphery of the reversible color change display body 1 obtained in Example 1 may be enclosed, this reversible color change display body 1 And a pen 6 having a fiber processing pen body, which is configured to accommodate water in the shaft cylinder as a water adhering means, to obtain a reversible color change display body set.
When the reversible color changing display body 1 was drawn in the white porous layer 3 with the pen 6 in a dry state, the porous layer 3 in that portion became transparent, and a red writing image was visually recognized. The written image was retained when the porous layer 3 was in a liquid-absorbing state, and when dried, it returned to its original white color and became invisible, and this phenomenon could be repeated many times.
Further, the pen can be stored in a storage portion 71 provided in the display body 1.
Furthermore, a magnet can be disposed on the back surface of the decorative case 7, which can be attracted to the magnetic wall surface, so that the place of use and convenience are expanded.

Example 3 (see FIG. 3)
A 1 mm thick rubber magnet (that is, rubber in which a magnetized magnetic material is dispersed) 22 is bonded to the back of a blue T / C broad fabric (65% Tetron, 35% cotton) 21 having a basis weight of 110 g / m ^2. 15 parts wet type silicic acid [trade name: Nipseal E-200, manufactured by Nippon Silica Industry Co., Ltd.], urethane emulsion [trade name: Hydran HW-930, Dainippon Manufactured by Ink Chemical Co., Ltd., solid content 50%] 30 parts, water 50 parts, silicone-based antifoaming agent 0.5 part, water-based ink thickener 3 parts, ethylene glycol 1 part, isocyanate-based crosslinking agent 3 parts Using a white screen printing ink that is uniformly mixed and stirred, solid printing is performed on a 100-mesh screen plate, and drying and curing is performed at 70 ° C. for 60 minutes to form the porous layer 3 to form a sheet-like reversible sheet. Strange A chromaticity display 1 was obtained.
When the reversible color change display body 1 is in a dry state, a white porous layer 3 is visually recognized. However, when water is attached, the porous layer 3 changes from a white opaque state to a transparent state due to liquid absorption. The blue color of the support (T / C broad fabric 21) is visually recognized and maintained in the liquid absorption state, but reversibly changes to the original white state by evaporating and drying the water. This phenomenon could be repeated many times.
Further, since the reversible color change display body 1 has magnetism on the porous layer 3 side, magnets and other magnetic bodies can be adsorbed on the surface of the porous layer.

Example 4
A reversible color change display body 1 obtained in Example 3, a pen that can accommodate water as a water adhering means in a shaft cylinder, and a fiber processing pen body is provided. A reversible color-change display body set was obtained by combining with steel paper (a magnetic body formed by attaching coated paper to both front and back surfaces of a metal foil).
When the reversible color changing display body 1 was drawn with a pen on the white porous layer 3 in a dry state, the porous layer 3 in that portion was changed to a transparent state, and blue characters were visually recognized. The written image (characters) was retained when the porous layer 3 was in a liquid-absorbing state, and when dried, it returned to its original white color and became invisible, and this phenomenon could be repeated many times.
In addition, since the reversible color change display body 1 can be used while adsorbed to another magnetic surface, writing in an adsorbed state on a wall surface or the like is possible, and the applicability is further enhanced.
Furthermore, it was possible to play by attaching the automobile type steel paper to the surface of the porous layer 3 side.

Example 5 (see FIG. 4)
From the soft oil-based resin on the surface of the support 2 provided with the magnetic layer 22 formed by applying an adhesive obtained by dispersing iron powder on the back surface of a white nylon taffeta fabric 21 having a basis weight of 80 g / m ^2. Using the ink for pink screen printing, solid printing was performed on a 180 mesh screen plate and dried and cured at 100 ° C. for 3 minutes to provide a colored layer 5 (wherein the colored layer 5 functions as a waterproof layer) Also demonstrates).
Subsequently, 15 parts of wet-process silicic acid [trade name: NIPSEAL E-200, manufactured by Nippon Silica Kogyo Co., Ltd.], 0.5 parts of blue pigment, urethane emulsion [trade name: Hydran HW- 930, manufactured by Dainippon Ink & Chemicals, Inc., solid content 50%] 30 parts, water 50 parts, silicone-based antifoaming agent 0.5 part, water-based ink thickener 3 parts, ethylene glycol 1 part, blocked isocyanate Using a blue screen printing ink obtained by uniformly mixing and stirring 3 parts of a cross-linking agent, solid printing is performed on a 100 mesh screen plate, followed by drying and curing at 130 ° C. for 5 minutes to form a porous layer 3. Thus, a reversible color change display 1 was obtained.
When the reversible color change display body 1 is in a dry state, a light blue porous layer 3 is visually recognized. However, when water is attached, the porous layer 3 changes from a light blue opaque state to a blue transparent state by liquid absorption. The purple color due to the color mixture with the lower colored layer 5 is visually recognized, and this state is maintained in the liquid absorption state, but reversibly changes to the original light blue state by evaporating and drying the water. This phenomenon could be repeated many times.
Further, since the reversible color changing display 1 has magnetism on the porous layer 3 side, magnets can be adsorbed on the surface of the porous layer.

Example 6
A reversible color-changing display body set obtained by combining the reversible color-changing display body 1 obtained in Example 5 and a pen that is configured to be capable of containing water as a water adhering means in a shaft cylinder and provided with a fiber processing pen body. Got.
When the reversible color change display body 1 draws characters with a pen on the light blue porous layer 3 in a dry state, the porous layer 3 in that portion changes to a blue transparent state, and the lower colored layer 5 A purple handwritten image due to the color mixture was visually recognized. The written image was retained when the porous layer 3 was in a liquid-absorbing state, and when dried, it returned to its original light green color and became invisible, and this phenomenon could be repeated many times.
Moreover, since the reversible color changing display body 1 has flexibility, it can be bent or rounded when stored.

Example 7 (see FIG. 5)
A resin molded body formed by integrally molding a plate-shaped flat portion having a length of 20 cm and a width of 30 cm and a three-dimensional molded portion formed around the plate-shaped flat portion with a polystyrene resin in which iron powder and a green pigment are dispersed. 2 on the surface of the plate-like planar portion of the support 2, 15 parts of wet method silicic acid [trade name: Nipseal E-200, manufactured by Nippon Silica Kogyo Co., Ltd.], urethane emulsion [trade name: Hydran AP-10, Dai Nippon Ink Chemical Co., Ltd., solid content 30%] 50 parts, water 50 parts, ethyl alcohol 10 parts, silicone antifoaming agent 0.5 parts, isocyanate crosslinking agent 3 parts uniformly mixed and stirred Using the above white screen spray ink, the entire surface was spray-coated and dried and cured at 40 ° C. for 24 hours to form a porous layer 3 to obtain a reversible color change display 1.
In the reversible color change display 1, the white porous layer 3 is visually recognized on the entire surface in a dry state. However, when water is attached, the porous layer 3 changes from a white opaque state to a transparent state due to liquid absorption. The green color of the molded body 2 is visually recognized, and the state is maintained in the liquid absorption state, but reversibly changes to the original white state by evaporating and drying the water. This phenomenon could be repeated many times.
Moreover, since the reversible color change display body 1 has magnetism on both the porous layer 3 side and the three-dimensional molded part, magnets can be adsorbed.

Example 8
The reversible color-changing display body 1 obtained in Example 7, a stamp tool provided with a felt material impregnating a liquid as a water adhering means, and a toy having a magnet disposed on the lower surface of a resin molded product imitating a car In combination, a reversible color change display set was obtained.
When the reversible color change display body 1 was imprinted on the white porous layer 3 in a dry state, the porous layer 3 in that portion was changed to a transparent state, and the green imprint of the lower layer was visually recognized. The imprint was retained when the porous layer 3 was in a liquid-absorbing state, and when dried, it returned to its original white color and became invisible, and this phenomenon could be repeated many times.
Furthermore, the car toy can be attached to the porous layer 3 and the three-dimensional molded part and played.

Example 9 (see FIG. 6)
A support 2 is prepared by sticking 0.1 mm thick coated paper 21 to both sides of an iron foil 22 having a thickness of 0.1 mm with an adhesive, and cyan, magenta and yellow are formed on both sides of the support 2. The pattern and the background color were printed on the entire surface using ultraviolet curable offset printing ink consisting of four colors of black, and cured by ultraviolet irradiation to provide a colored layer 5 (note that the colored layer 5 is a waterproof layer) Also demonstrates the function).
Subsequently, 15 parts of wet process silicic acid [trade name: Nipseal E-200, manufactured by Nippon Silica Industry Co., Ltd.], urethane emulsion [trade name: Hydran HW-930, Dainippon Ink & Chemicals, Inc.] ), 50% solids] 30 parts, 50 parts water, 0.5 parts silicone antifoaming agent, 3 parts thickener for aqueous ink, 1 part ethylene glycol, 3 parts isocyanate crosslinking agent, Using the green screen printing ink obtained by stirring, the solid layer is partially printed on a 100 mesh screen plate, dried and cured at 80 ° C. for 3 minutes to form the porous layer 3, and sheet-like reversible discoloration. A display 1 was obtained.
In the reversible color change display 1, in the dry state, the design and background color of the colored layer 5 and the white porous layer 3 that conceals part of the colored layer 5 are visually recognized. When adhered, the colored layer 5 that has been concealed by the porous layer 3 can be visually recognized by changing from a white opaque state to a transparent state due to liquid absorption. This state is maintained in the liquid absorption state, but the water returns to the original white state by evaporating and drying, and the lower layer of the porous layer 3 is concealed. This phenomenon could be repeated many times.
Further, since the entire reversible color change display body 1 has magnetism on the entire porous layer side, magnets can be adsorbed on the surfaces of the porous layer 3 and the colored layer 5.

Example 10
The reversible color-changing display body 1 obtained in Example 9 and a pen that can accommodate water in the shaft cylinder as a water adhering means, and provided with a fiber processing pen body (further, a magnet is formed on a part of the shaft cylinder) To provide a reversible color-change display body set.
In the reversible color change display 1, the design and background color of the colored layer 3 and the white porous layer 3 concealing a part of the colored layer 3 are visually recognized in the dry state. When water was allowed to adhere with the pen, the porous layer 3 at that portion changed to a transparent state, and the lower colored layer 5 was visually recognized. The phenomenon was maintained when the porous layer 3 was in the liquid absorption state, and when dried, it returned to its original white color and became invisible, and this phenomenon could be repeated many times.
In addition, since the reversible color change display body 1 has flexibility, it can be bent or rounded when stored, and the pen can be adhered and held.

Example 11 (see FIG. 7)
The support 2 is formed by applying an ink in which iron powder and a red pigment are dispersed to the surface of the block-shaped polypropylene resin molded body 21, and wet-type silicic acid [trade name: nip seal] on the ink surface (magnetic layer 22). E-200, manufactured by Nippon Silica Industry Co., Ltd.] 15 parts, urethane emulsion [trade name: Hydran AP-10, manufactured by Dainippon Ink & Chemicals, Inc., solid content 30%] 50 parts, water 50 parts, ethyl alcohol 10 parts, 0.5 parts of silicone antifoaming agent and 3 parts of isocyanate crosslinking agent are uniformly mixed and stirred using white screen spray ink and spray-dried at 40 ° C for 24 hours. Thus, the porous layer 3 was formed to obtain the reversible color change display body 1.
In the reversible color change display 1, the white porous layer 3 is visually recognized on the entire surface in a dry state. However, when water is attached, the porous layer 3 changes from a white opaque state to a transparent state due to liquid absorption. Although red is visually recognized and maintained in the liquid absorption state, the water reversibly changes to the original white state by evaporating and drying. This phenomenon could be repeated many times.
Further, since the reversible color changing display 1 has magnetism on the porous layer 3 side, magnets can be adsorbed.

Example 12
A reversible color-changing display body set obtained by combining the reversible color-changing display body 1 obtained in Example 11 with a pen that can accommodate water as a water adhering means in a shaft cylinder and is provided with a fiber processing pen body. Got.
When the reversible color change display body 1 was written on the white porous layer 3 in a dry state, the porous layer 3 at that portion changed to a transparent state, and a red imprint was visually recognized. The handwriting was retained when the porous layer 3 was in a liquid-absorbing state, and when dried, it returned to its original white color and became invisible, and this phenomenon could be repeated many times.

Example 13
A white oil-based resin is applied on a surface of a 1 mm thick iron plate (magnetic support 2) to provide a waterproof layer 4, and then a white color obtained by providing a pink colored layer 5 on the waterproof layer 4. 100% cotton satin fabric. Next, 15 parts wet-type silicic acid [trade name: Nipsil E-200, manufactured by Nippon Silica Industry Co., Ltd.], urethane emulsion [trade name: Hydran HW-930, manufactured by Dainippon Ink & Chemicals, Inc., solid content 50% ] White screen obtained by uniformly mixing and stirring 30 parts, 50 parts of water, 0.5 part of a silicone-based antifoaming agent, 3 parts of a thickener for water-based ink, 1 part of ethylene glycol, and 3 parts of a blocked isocyanate-based crosslinking agent Using a printing ink, solid printing was performed on a 100-mesh screen plate, and the water-discoloring fabric formed by drying and curing at 130 ° C. for 5 minutes to form the porous layer 3 was adhered with an adhesive to form a sheet. A reversible color change display 1 was obtained.
In the reversible color change display body 1, the white porous layer 3 is visually recognized on the substantially entire surface in a dry state. However, when water is attached, the porous layer 3 changes from a white opaque state to a colorless and transparent state by liquid absorption. The pink color of the lower layer is visually recognized and maintained in the liquid absorption state, but when the water evaporates and drys, it changes to the original white state.
Further, since the reversible color changing display 1 has magnetism on the porous layer 3 side, magnets can be adsorbed on the surface of the porous layer.

Example 14
After disposing a decorative case made of a resin molded body (including a storage part) on the iron plate side so as to surround the outer periphery of the reversible color change display body 1 obtained in Example 13, the reversible color change display body 1 and A reversible color-changing display body set was obtained by combining with a pen that can accommodate water in the shaft tube as a water adhering means and provided with a fiber processing pen body.
When the reversible color changing display body 1 was drawn with a pen on the white porous layer 3 in a dry state, the porous layer 3 in that portion became transparent and a pink writing image was visually recognized. The written image was retained when the porous layer 3 was in a liquid-absorbing state, and when dried, it returned to its original white color and became invisible, and this phenomenon could be repeated many times.
Further, the pen can be stored in a storage section provided in the display body 1.
Furthermore, a magnet can be disposed on the back surface of the decorating case, which can be attracted to the magnetic wall surface, so that the place of use is expanded.

It is a longitudinal cross-sectional explanatory drawing of the reversible color-change display body of this invention. It is a front view of the reversible color-change display body of FIG. It is longitudinal cross-sectional explanatory drawing of another reversible color-change display body of this invention. It is longitudinal cross-sectional explanatory drawing of another reversible color-change display body of this invention. It is longitudinal cross-sectional explanatory drawing of another reversible color-change display body of this invention. It is longitudinal cross-sectional explanatory drawing of another reversible color-change display body of this invention. It is longitudinal cross-sectional explanatory drawing of another reversible color-change display body of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Reversible color-change display body 2 Magnetic support 21 Base material 22 Magnetic layer 3 Porous layer 4 Waterproof layer 5 Colored layer 6 Pen (water adhesion means)
7 decoration case 71 storage part

Claims (5)

A porous support layer made of a plate-like magnetic material and having a low refractive index pigment fixed to a binder resin in a dispersed state and having different transparency in a liquid-absorbing state and a non-liquid-absorbing state is provided. In addition, the reversible discoloration display body having a magnetic surface on the porous layer side, and a writing instrument or applicator applied with a plastic porous body or fiber processed body having continuous pores as a nib member, or a stamp tool is selected. A reversible color-changing display body set comprising at least one water adhering means and a magnet. The reversible color-changing display body set according to claim 1, wherein a colored layer is interposed between the support and the porous layer. The reversible color-change display body set according to claim 1 or 2, wherein a waterproof layer is interposed between the support and the porous layer. The reversible color-changing display body set according to claim 3, wherein the waterproof layer is colored. The reversible color-changing display body set according to claim 1, wherein the water adhering means includes a magnet.

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