JP2020199708A - Discoloring body and discoloring body set - Google Patents

Abstract

To provide: a discoloring body with which a concealed color image is difficult to see in a dry state and the colored image is clearly visible in a liquid absorption state; and a discoloring body set.SOLUTION: Each of a discoloring body 1 and a discoloring body set includes a colored image 3, a porous layer 4 and a porous image 5 which are located on a substrate 2. The porous layer is designed to conceal the colored image by being colored opaque in a dry state in which a low refractive index pigment and a coloring agent are dispersedly fixed together with a binder resin on the colored image, and is designed to make the colored image visible by being colored transparent in a liquid absorption state. The porous image is designed to conceal the colored image by being opaque in a dry state in which a low refractive index pigment is dispersedly fixed together with a binder resin on the porous layer located on a region where colored image is disposed, and is designed to make the colored image visible by being transparent in a liquid absorption state. A ratio of an area of a region where the porous layer is visible in the dry state and an area where the porous image is visible in the dray state is in a range of 20:80 to 80:20.SELECTED DRAWING: Figure 1

Description

The present invention relates to a discolored body and a discolored body set. More specifically, the present invention relates to a discolored body and a discolored body set in which a concealed image is difficult to discriminate in a dry state and the concealed image is clearly visible in a state of absorbing a liquid such as water.

Conventionally, as a sheet for visually recognizing different images in a dry state and a water absorption state, a coating layer containing a low refractive index pigment and a transparent film having a surface image provided on the coating layer are bonded to a mount having an image on a colored surface. A water image sheet is disclosed (see, for example, Patent Document 1).
In the water image sheet, since the image of the lower layer is hidden by the coating layer in the dry state, only the surface image is visible, the coating layer becomes transparent in the liquid absorbing state, and the surface image is the color tone of the mount or the image of the lower layer. It is configured so that it becomes difficult to be visually recognized in synchronization and only the lower layer image is visible, and even if a different image is visually recognized, in order to synchronize the surface image with the lower layer image and / or the color tone of the mount. It is necessary to make the color similar or light, and to make sure that the surface image and the lower layer image do not overlap as much as possible. Therefore, it is difficult to visually recognize the image of the lower layer in the dry state, and it is not suitable for the configuration in which the image is clearly visible in the liquid absorbing state.

Japanese Unexamined Patent Publication No. 63-260476

The present invention is intended to solve the problems of the conventional water image sheet, that is, the concealed colored image is difficult to see in the dry state, and the colored image is clearly visible in the liquid absorbing state. It is intended to provide a discolored body and a discolored body set.

In the present invention, a colored image is formed on a support, and a low refractive index pigment and a coloring agent are fixed on the colored image together with a binder resin in a dispersed state, and the colored image is opaque to be colored and opaque to hide the colored image in a liquid absorbing state. The colored image is opaque in a dry state in which a low refractive index pigment is fixed together with a binder resin on a porous layer that is colored and transparent to make the colored image visible, and a portion where the colored image is provided. A porous image that is concealed and made transparent in a liquid absorbing state so that the colored image can be visually recognized is provided, and the area of the portion where the porous layer is visible in the dry state and the porous image are visually recognized in the dry state. A discolored body having an area ratio of 20:80 to 80:20 is required.
Furthermore, the area ratio of the area where the porous layer is visible in the dry state to the area where the porous image is visible in the dry state is in the range of 30:70 to 70:30, and the coloring. The dry color density (D1) of the porous layer provided on the image, the dry color density (D2) of the porous layer provided on the support, and the porous image provided on the porous layer. The dry color density (D3) satisfies the formulas (1) and (2).
0 ≦ D1-D2 <1.0 (1)
0 <D2-D3 (2)
A question display unit is provided around the porous layer, the colored image is the correct answer of the question display unit, a plurality of question display units and a plurality of colored images are provided, and characters of the colored image. Characters whose size is in the range of 3 to 13 points, the colored image is a process print image, the problem display part is a map, the colored image is a place name, and the problem display part is a national flag. Yes, it is a requirement that the colored image is the name of the country.
Further, a discoloration body set including a discoloration body and a water adhering tool is required.

The present invention has excellent applicability to various fields such as toy field, decoration field, design field, etc., because the hidden colored image is hard to be visually recognized in the dry state and the colored image is clearly visible in the liquid absorbing state. It is possible to provide a discolored body and a discolored body set.

It is a vertical cross-sectional explanatory view of one Example of the discolored body of this invention.

The present invention uses a discolored body in which different aspects are visually recognized in a dry state and in a state of absorbing a liquid such as water, and the appearance of being visually recognized in a state of absorbing liquid is difficult to distinguish in a dry state. There is a discoloration body set, which will be explained below.

The support is effective as long as it is a base material having printability, for example, cloth such as paper, synthetic paper, woven fabric, knitted fabric, braid, non-woven fabric, natural or synthetic leather, plastic, glass, ceramics, metal. , Wood, stone, etc. are used. Further, the shape is preferably flat, but may be uneven.

A colored image is provided on the support.
The colored image is formed of a binder resin containing a colorant.
Examples of the colorant include general dyes, general pigments, fluorescent dyes, fluorescent pigments, metallic luster pigments and the like.
The colorant forms a colored image by applying an ink or paint contained in a vehicle containing a binder resin as a binder to a support and then drying the volatile matter.
Examples of the binder resin include urethane resin, nylon resin, vinyl acetate resin, acrylic acid ester resin, acrylic acid ester copolymer resin, acrylic polyol resin, vinyl chloride-vinyl acetate copolymer resin, maleic acid resin, polyester resin, and 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. Examples thereof include resin emulsions, caseins, starches, cellulose derivatives, polyvinyl alcohols, urea resins, phenol resins and the like.
The colored image is a printing means such as process printing, screen printing, offset printing, gravure printing, coater, tampo printing, inkjet printing, transfer, brush coating, spray coating, electrostatic coating, electrodeposition coating, sink coating, roller coating. , Is formed on the support by dipping coating or the like.
Further, an ink or paint contained in a vehicle containing a colorant and a binder resin as a binder is applied in advance on another base material to provide a transfer layer, and the transfer layer is transferred onto a support to obtain a colored image. Can also be provided.
The colored image can be made into a multicolored image by using a plurality of colorants having different colors, and the colorful image can be visually recognized, so that the commercial value can be enhanced.
Further, when the support has transparency, a colored image can be provided on the back surface of the support (the surface on which the porous layer and the porous image are not provided).
The colored image includes various characters, numbers, symbols, figures, a large number of parallel lines, crossing lines, a honeycomb shape formed by a combination of lines, a mesh shape, a grid shape, a grid shape, a turtle shell pattern, and other geometric patterns. , People, animals, plants, fruits, groceries, vehicles, buildings, celestial bodies, etc.

The porous layer is a layer in which a low refractive index pigment and a colored image are fixed together with a binder resin in a dispersed state, and is colored opaque in a dry state to conceal the lower layer, thereby hindering the visibility of the colored image and making the colored image colored. Since it is presented, the porous image described later can be clearly seen.
As the colorant, the same colorant as that used for the colored image can be used.
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, and these have a refractive index of 1.4 to 1. It is in the range of 1.8 and shows good transparency when it absorbs water.
Examples of the salt of silicic acid include aluminum silicate, potassium aluminum silicate, sodium aluminum silicate, aluminum calcium silicate, potassium silicate, calcium silicate, sodium calcium silicate, sodium silicate, magnesium silicate, potassium magnesium silicate and the like.
Examples of the low refractive index pigment preferably used include silicic acid and silicate.
Further, two or more kinds of the low refractive index pigments can be used in combination.
The particle size of the low refractive index pigment is not particularly limited, but those having a particle size of 0.03 to 10.0 μm are preferably used.
The silicic acid may be a silicic acid produced by a dry method, but a silicic acid produced by a wet method (hereinafter referred to as a wet method silicic acid) is particularly effective. Explaining this point, the silicic acid is amorphous. It is produced as a quality amorphous silicic acid, and depending on the production method, a dry method using a vapor phase reaction such as thermal decomposition of silicon halide such as silicon tetrachloride (hereinafter referred to as dry silicic acid) and sodium silicate It is roughly divided into the wet method using a liquid phase reaction such as decomposition with an acid such as, and the structure is different between the dry method silicic acid and the wet method silicic acid, and the dry method silicic acid has a three-dimensional structure in which silicic acid is tightly bonded. On the other hand, the wet method silicic acid has a so-called two-dimensional structural portion in which silicic acid is condensed to form a long molecular arrangement.
Therefore, since the molecular structure is coarser than that of the dry silicic acid, when the wet silicic acid is applied to the porous layer, the diffuse reflection of light in the dry state is excellent as compared with the system using the dry silicic acid. It is presumed that the concealment property under normal conditions will increase.
Further, since the porous layer mainly absorbs water, the wet silicic acid has more hydroxyl groups existing as silanol groups on the particle surface than the dry silicic acid, and has a high degree of hydrophilicity. , Suitable for use.
In addition, in order to adjust the hiding property of the porous layer in a normal state and the transparency in a liquid absorbing state, another low refractive index pigment can be used in combination with the wet method silicic acid.

The low refractive index pigment in the porous layer depends on properties such as particle size, specific surface area, and oil absorption, but in order to satisfy both the hiding property in the normal state and the transparency in the liquid absorbing state, it is necessary. preferably the coating amount is 1 to 30 g / ^{m 2,} more preferably 5 to 20 g / ^{m 2.} If it is less than 1 g / m ² , it is difficult to obtain sufficient hiding property under normal conditions, and if it exceeds 30 g / m ² , it is difficult to obtain sufficient transparency at the time of liquid absorption.
The low refractive index pigment and the colorant are dispersed in a vehicle containing a binder resin as a binder, applied on a support, and then dried to form a porous layer.
Examples of the binder resin include urethane resin, nylon resin, vinyl acetate resin, acrylic acid ester resin, acrylic acid ester copolymer resin, acrylic polyol resin, vinyl chloride-vinyl acetate copolymer resin, maleic acid resin, polyester resin, and 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. Examples thereof include resin emulsions, caseins, starches, cellulose derivatives, polyvinyl alcohols, urea resins, phenol resins and the like.
The mixing ratio of the low refractive index pigment and the binder resin depends on the type and properties of the low refractive index pigment, but preferably, the binder resin solid content is 0.5 to 2 mass with respect to 1 part by mass of the low refractive index pigment. It is a part, more preferably 0.8 to 1.5 parts by mass. When the solid content of the binder resin is less than 0.5 parts by mass with respect to 1 part by mass of the low refractive index pigment, it is difficult to obtain a practical film strength of the porous layer, and when it exceeds 2 parts by mass. In addition, the permeability of water into the porous layer is likely to be impaired.
Since the mixing ratio of the binder resin to the colorant is smaller in the porous layer than in a general coating film, it is difficult to obtain sufficient film strength. Therefore, it is effective to use a nylon resin or a urethane-based resin among the above-mentioned binder resins in order to increase the scratch resistance.
Examples of the urethane-based resin include polyester-based urethane resin, polycarbonate-based urethane resin, and polyether-based urethane resin, and two or more of them can be used in combination. Further, a colloid in which the resin is emulsified and dispersed in water or self-emulsified by the ionic group of the ionic urethane resin (urethane ionomer) itself without the need for an emulsifier and dissolved or dispersed in water. A dispersed type (ionomer type) urethane resin can also be used.
As the urethane-based resin, either an aqueous urethane-based resin or an oil-based urethane-based resin can be used, but an aqueous urethane-based resin, particularly a urethane-based emulsion resin or a colloid-dispersed urethane-based resin is preferably used.
The urethane-based resin can be used alone, but other binder resins can also be used in combination depending on the performance required for the film. When a binder resin other than the urethane resin is used in combination, it is preferable that the urethane resin is contained in the binder resin of the porous layer in a solid content mass ratio of 30% or more in order to obtain a practical film strength.
Among the binder resins, those having a crosslinkable property can be further improved in film strength by adding an arbitrary cross-linking agent and cross-linking.
The binder resin has different affinities with water, and by combining these, the permeation time into the porous layer, the degree of permeation, and the slow speed of drying after permeation can be adjusted. Further, the adjustment can be controlled by appropriately adding a dispersant or a surfactant.

The porous layer can be coated by screen printing, offset printing, gravure printing, coater, tampo printing, transfer or other printing means, brush coating, spray coating, electrostatic coating, electrodeposition coating, sink coating, roller coating, dip coating, etc. Can be formed.

On the porous layer where the colored image is provided, a low refractive index pigment is fixed together with a binder resin in a dispersed state to make it opaque in a dry state to hide the colored image, and to make it transparent in a liquid absorbing state to make the colored image transparent. A porous image is provided so that the image can be visually recognized.
In order to make the colored image clearly visible, it is conceivable to increase the density of the colored image and reduce the amount of low refractive index pigment contained in the porous layer, but on the other hand, the porous layer is in a dry state. Does not show sufficient concealment.
The porous image is an image in which a low refractive index pigment is fixed together with a binder resin in a dispersed state, and is opaque in a dry state to visually recognize a white porous image, and the porous layer is completely colored in a dry state. It is possible to give the effect of visually concealing even if the is not concealed. That is, the porous image partially conceals the afterimage due to the colored image (colored image visually recognized through the porous layer in a dry state), and visually camouflages the afterimage of the portion where the porous image is not provided. Has an effect.
As the low refractive index pigment and the binder resin, the same low refractive index pigment and the binder resin used for the porous layer can be used.
The porous image can be formed by the same method as that for the porous layer.
In the discolored body obtained as described above, in the liquid absorbing state, the porous image becomes transparent and invisible, and the porous layer also becomes colored and transparent, so that the colored image is visible. The color of the colored image visually recognized in the liquid absorbing state is a color mixed with the color of the porous layer.
Therefore, the porous image in the dry state and the colored image in the liquid absorbing state can be selectively visually recognized.

The area ratio of the area where the porous layer is visible in the dry state to the area where the porous image is visible in the dry state is 20:80 to 80:20, preferably 30:70 to 70:30. More preferably, it is in the range of 40:60 to 60:40.
By satisfying the area ratio, the porous image can sufficiently conceal the afterimage due to the colored image and sufficiently exhibit the effect of visually camouflaging the afterimage.

Further, the dry color density (D1) of the porous layer provided on the colored image, the dry color density (D2) of the porous layer provided on the support, and the dry color density (D2) provided on the support are provided. It is preferable that the dry color density (D3) of the porous image satisfies both the formulas (1) and (2), and the colors of the porous layer provided on the colored image and the porous layer provided on the support. Even if there is a difference in the densities represented by the formula (1), the dry color density (D2) of the porous layer provided on the support and the dry color density of the porous image provided on the porous layer When (D3) has the difference represented by the formula (2), the effect of visually camouflaging the afterimage can be further exhibited.
The formula (1) is preferably 0 ≦ D1-D2 <0.5, and the formula (2) is preferably 0.1 ≦ D2-D3.
The dry color density (D1) of the porous layer provided on the colored image, the dry color density (D2) of the porous layer provided on the support, and the porous image provided on the porous layer. The color density (D3) in the dry state was the sum of the K value, C value, M value, and Y value of the densities measured by the fluorescence spectrophotometer FD-7 manufactured by Konica Minolta.

A problem display section is provided around the porous layer of the discolored body (around the overprinted printing section of the colored image, the porous layer, and the porous image), and the colored image is the correct answer of the problem display section. Thereby, a discolored body suitable as an educational tool, an educational toy, a training tool, and a training toy can be obtained.
In a system in which a question display unit is provided around the porous layer and the colored image is the correct answer of the problem display unit, by providing a plurality of problem display units and a plurality of colored images, practical use of intellectual education and training. It is possible to obtain a discolored body rich in sex.
A discolored body having a plurality of problem display units and a plurality of colored images has excellent formability of a plurality of colored images by using characters having a character size in the range of 4 to 12 points of the colored images, and is intellectually educated. In addition to being able to obtain a discolored body that is highly practical in training, the colored image is a process printed image, so that the clarity of the image is excellent.
Specifically, as the educational tool, educational toy, training tool, and training toy, the problem display part is a map, the colored image is a discolored body whose place name is a place name, the problem display part is a national flag, and the colored image is a country name. There is a discoloration body.

Specific embodiments of the discolored body include, for example, doll costumes such as stuffed animals, dolls, and doll dresses, doll accessories such as bags, water gun targets, animal-like models, and human and doll handprints. Examples include toys such as boards that show evidence of foot shapes, training tools such as water brush sheets, clothing such as dresses and swimwear, shoes, bags, furniture, artificial flowers, coasters, and the like.
It can also be applied as various indicators, such as liquid leakage detection for pipes, pipes, water tanks, tanks, etc., water wetting detection for personal belongings and furniture, water wetting detection for transporting and storing water-prohibited chemicals, and dew condensation. , Detection of urine in disposable diapers, detection of moisture in soil, etc.

As a means for adhering water to the discolored body, it is possible to directly immerse the discolored body in water, wet the hands and fingers with water and bring them into contact with each other, or apply a water adhering tool.
Examples of the water adhering tool include a water gun, a sprayer, a writing or coating tool having a brush tip or a fiber pen body at the tip, a fiber body or a brush that stores water in a container and derives water in the container. Examples include writing or coating tools, stamping tools, etc. provided with.
As the water adhering tool, a writing tool or a coating tool to which a plastic porous body or a fiber processed body having continuous pores is applied as a pen tip member can easily form a writing image and enhance practicality.
It should be noted that the discolored body set can also be formed by combining the water adhering tool and the discolored body.

Examples are shown below, but the present invention is not limited thereto.
In addition, the part in an Example shows a mass part.
Example 1 (see FIG. 1)
Fabrication of discolored material Process printing with an offset printing machine using cyan, magenta, yellow, and black non-discoloring ultraviolet curable offset printing inks on white synthetic paper as the support 2 (resolution: 180 lines, 350 dpi) Then, a black colored image 3 composed of the 12-point character "Tokyo" and the character "Tokyo" consisting of the 6-point offset kana was formed in the upper part of the character.
Next, on the colored image 3, 15 parts of wet silicone (trade name: Nipseal E-200, manufactured by Nippon Silica Industry Co., Ltd.), blue pigment [trade name: Sundai Super Blue F707-E, Sanyo Dye Co., Ltd.] Manufactured by 0.4 parts, Urethane emulsion [Product name: Hydran HW-930, manufactured by Dainippon Ink and Chemicals Co., Ltd., solid content 50%] 30 parts, water 40 parts, silicone-based defoamer 0.5 parts, Solid printing is performed on the entire surface with a 100-mesh screen plate using a blue screen printing ink obtained by uniformly mixing and stirring 3 parts of a thickener for water-based ink, 1 part of ethylene glycol, and 1 part of an isocyanate-based cross-linking agent. , 70 ° C. was dried and cured for 5 minutes to form the porous layer 4.
Next, on the porous layer 4, 12 parts of wet silicone (trade name: Nipseal E-200, manufactured by Nippon Silica Industry Co., Ltd.), urethane emulsion [trade name: Hydran HW-930, Dainippon Ink and Chemicals Co., Ltd. ( Made by Co., Ltd., solid content 50%] 30 parts, water 35 parts, silicone-based defoamer 0.5 parts, water-based ink thickener 3 parts, ethylene glycol 1 part, isocyanate-based cross-linking agent 1 part are uniformly mixed. , Using a white screen printing ink that has been stirred, print on a screen plate with a dot pattern of 150 mesh, and dry and cure at 70 ° C. for 5 minutes to form a porous image 5 with a dot pattern. Got
The area ratio of the area where the porous layer was visually recognized in the dry state to the area where the porous image was visually recognized in the dry state was 50:50.
A map of Japan is printed on the support as a problem display unit, and an overprint printing unit of the colored image, the porous layer, and the porous image is provided in the vicinity of the position of Tokyo on the Japanese map, and the coloring is performed. The image is the correct answer for the question display.
The dry color density (D1) of the porous layer provided on the colored image shown by A in FIG. 1 is 1.31 (K: 0.38, C: 0.64, M: 0.20). , Y: 0.09), the dry color density (D2) of the porous layer provided on the support shown in FIG. 1B is 1.19 (K: 0.36, C: 0.64, M: 0.16, Y: 0.03), the dry color density (D3) of the porous image provided on the porous layer shown by C in FIG. 1 is 0.22 (K: 0.07, C: 0.10, M: 0.04, Y: 0.01), D1-D2 = 0.12, and D2-D3 = 0.97.

In the dry state, the discolored body has a porous image of white dots (white dots on a blue background) on a pastel blue porous layer near Tokyo on a map of Japan, but water When water is attached using the included brush, the porous image becomes transparent and the porous layer becomes blue and transparent, so that the entire surface becomes blue, and the blue of the porous layer and the black of the colored image become black. The mixed dark blue characters "Tokyo" and "Tokyo" appeared.
The above-mentioned aspect showed this state for 3 minutes in a room at 25 ° C. and 50% humidity, but as it dried, the porous layer and the porous image gradually became opaque, and the letters "Tokyo" and "Tokyo" were displayed. Was hard to see, and a white dot pattern appeared, and after 5 minutes, it became a state before water was attached, that is, a white dot pattern on a blue background, and the characters became invisible.
The above-mentioned aspect change can be repeated many times by adhering water, and is useful as an educational toy or a training toy.

Example 2
Preparation of discolored body set Discoloration with excellent portability by combining the discolored body of Example 1 with a pen having a fiber pen body or the like at the tip as a means for adhering water and having a structure capable of accommodating water in a barrel. I got a body set.
When writing with the pen containing water in the white dot pattern on the blue background of the discolored body, the characters "Tokyo" and "Tokyo" appeared.
The above-mentioned aspect showed this state for 3 minutes in a room at 25 ° C. and 50% humidity, but as it dried, the porous layer and the porous image gradually became opaque, and the letters "Tokyo" and "Tokyo" were displayed. Was hard to see, and a white dot pattern appeared, and after 5 minutes, it became a state before water was attached, that is, a white dot pattern on a blue background, and the characters became invisible.
The above-mentioned aspect change can be repeated many times by adhering water, and is useful as an educational toy or a training toy.

Example 3
Fabrication of discolored material Process printing (resolution: 180 lines, 350 dpi) on white synthetic paper as a support using cyan, magenta, yellow, and black non-discoloring ultraviolet curable offset printing inks with an offset printing machine. A blue colored image consisting of the 7-point character "Japan" and the character "Nihon" consisting of the 4-point offset kana was formed in the upper part of the character.
Next, on the colored image, 15 parts of wet silicone acid [trade name: Nipseal E-200, manufactured by Nippon Silica Industry Co., Ltd.], pink pigment [trade name: TC Rubin FR-H, Dainichi Seika Kogyo Co., Ltd. )] 1.0 part, urethane emulsion [trade name: Hydran HW-930, manufactured by Dainippon Ink and Chemicals Co., Ltd., solid content 50%] 30 parts, water 40 parts, silicone defoamer 0.5 parts , 3 parts of thickener for water-based ink, 1 part of ethylene glycol, and 1 part of isocyanate-based cross-linking agent are uniformly mixed and stirred, and the entire surface is solid with a 100-mesh screen plate using a pink screen printing ink. It was printed and dried and cured at 70 ° C. for 5 minutes to form a porous layer.
Next, on the porous layer, 12 parts of wet silicone (trade name: Nipseal E-200, manufactured by Nippon Silica Industry Co., Ltd.), urethane emulsion [trade name: Hydran HW-930, Dainippon Ink and Chemicals Co., Ltd.] ), Solid content 50%] 30 parts, 35 parts of water, 0.5 parts of silicone defoamer, 3 parts of thickener for water-based ink, 1 part of ethylene glycol, 1 part of isocyanate-based cross-linking agent are uniformly mixed. Using a white screen printing ink made by stirring, printing was performed on a screen plate having a polka dot pattern of 150 mesh, and the mixture was dried and cured at 70 ° C. for 5 minutes to form a porous image of the polka dot pattern to obtain a discolored product. ..
The area ratio of the area where the porous layer was visually recognized in the dry state to the area where the porous image was visually recognized in the dry state was 70:30.
The Japanese flag is printed on the support as a problem display unit, and an overprint printing unit of the colored image, the porous layer, and the porous image is provided in the vicinity of the Japanese flag, and the colored image is a problem. It is the correct answer on the display.
The dry color density (D1) of the porous layer provided on the colored image is 0.78 (K: 0.23, C: 0.14, M: 0.30, Y: 0.11). The dry color density (D2) of the porous layer provided on the support is 0.45 (K: 0.14, C: 0.01, M: 0.26, Y: 0.04), porous. The dry color density (D3) of the porous image provided on the layer is 0.29 (K: 0.06, C: 0.03, M: 0.18, Y: 0.02), and D1. -D2 = 0.33 and D2-D3 = 0.16.

In the dry state, a porous image of white polka dots (white polka dots on a pink background) is visible on a pastel-like pink porous layer near the Japanese flag, but water adheres to the discolored body. When water is adhered with the finger, the porous image becomes transparent and the porous layer becomes transparent in pink, so that the entire surface becomes pink, and the pink color of the porous layer and the blue color of the colored image become transparent. Characters consisting of the mixed pink "Japan" and "Tokyo" kana kana appeared.
The above-mentioned aspect showed this state for 3 minutes in a room with a temperature of 25 ° C. and a humidity of 50%, but as it dried, the porous layer and the porous image gradually became opaque, and from the okurigana of "Japan" and "Nihon". The characters become difficult to see and white polka dots appear, and after 5 minutes, the characters before the water adheres, that is, the white polka dots on the pink background, and the characters "Japan" and "Nihon" Characters consisting of kana are no longer visible.
The above-mentioned aspect change can be repeated many times by adhering water, and is useful as an educational toy or a training toy.

Example 4
Preparation of discolored body set Discoloration with excellent portability by combining the discolored body of Example 3 with a pen having a fiber pen body or the like at the tip as a means for adhering water and having a structure capable of accommodating water in a barrel. I got a body set.
When writing with the pen containing water in the white polka dot pattern on the pink background of the discolored body, the characters "Japan" and "Nihon" appeared.
The above-mentioned aspect showed this state for 3 minutes in a room at 25 ° C. and 50% humidity, but as it dried, the porous layer and the porous image gradually became opaque, and the letters "Japan" and "Nihon" were visible. Along with the fact that it became difficult to do so, a white polka dot pattern appeared, and after 5 minutes, it became a state before water was attached, that is, a white polka dot pattern on a pink background, and the characters became invisible.
The above-mentioned aspect change can be repeated many times by adhering water, and is useful as an educational toy or a training toy.

Example 5
Preparation of discolored material Process printing (resolution: 180 lines, 350 dpi) on white synthetic paper as a support using non-discoloring UV curable offset printing inks of cyan, magenta, yellow, and black with an offset printing machine. A black colored image consisting of the 6-point characters "Japan" and "United States" was formed.
Next, on each of the colored images, 15 parts of wet silicone (trade name: Nipseal E-200, manufactured by Nippon Silica Industry Co., Ltd.), blue pigment [trade name: Sundai Super Blue F707-E, Sanyo Dye Co., Ltd.] Manufactured by] 0.3 parts, Urethane emulsion [Product name: Hydran HW-930, manufactured by Dainippon Ink and Chemicals Co., Ltd., solid content 50%] 30 parts, water 40 parts, silicone-based defoamer 0.5 parts, Solid printing is performed on the entire surface with a 100-mesh screen plate using a blue screen printing ink obtained by uniformly mixing and stirring 3 parts of a thickener for water-based ink, 1 part of ethylene glycol, and 1 part of an isocyanate-based cross-linking agent. , 70 ° C. was dried and cured for 5 minutes to form a porous layer.
Next, on the porous layer, 12 parts of wet silicone (trade name: Nipseal E-200, manufactured by Nippon Silica Industry Co., Ltd.), urethane emulsion [trade name: Hydran HW-930, Dainippon Ink and Chemicals Co., Ltd.] ), Solid content 50%] 30 parts, 35 parts of water, 0.5 parts of silicone defoamer, 3 parts of thickener for water-based ink, 1 part of ethylene glycol, 1 part of isocyanate-based cross-linking agent are uniformly mixed. Using a white screen printing ink made by stirring, printing is performed on a screen plate with a check pattern of 150 mesh, and the mixture is dried and cured at 70 ° C. for 5 minutes to form a porous image of a lattice pattern to obtain a discolored product. It was.
The area ratio of the area where the porous layer was visually recognized in the dry state to the area where the porous image was visually recognized in the dry state was 80:20.
A world map is printed on the support as a problem display unit, and an overprint printing unit of the colored image, the porous layer, and the porous image is provided in the vicinity of the positions of Japan and the United States of America on the world map. The colored image is the correct answer for the question display section.
The dry color density (D1) of the porous layer provided on the colored image is 1.26 (K: 0.38, C: 0.59, M: 0.20, Y: 0.09). The dry color density (D2) of the porous layer provided on the support is 0.78 (K: 0.23, C: 0.42, M: 0.11, Y: 0.02), porous. The dry color density (D3) of the porous image provided on the layer is 0.18 (K: 0.06, C: 0.08, M: 0.03, Y: 0.01), and D1. -D2 = 0.48 and D2-D3 = 0.60.

In the dry state, the discolored body has a porous image of a white lattice pattern (white lattice pattern on a blue background) on a pastel blue porous layer near Japan and the United States of America on the world map, but water. When water is attached using a brush containing the above, the porous image becomes transparent and the porous layer becomes blue and transparent, so that the entire surface becomes blue, and the blue of the porous layer and the black of the colored image. The dark blue characters "Japan" and "United States", which are mixed colors, appeared.
The above-mentioned aspect showed this state for 3 minutes in a room at 25 ° C. and 50% humidity, but as it dried, the porous layer and the porous image gradually became opaque, and the letters "Japan" and "United States" were visible. A white checkerboard pattern appeared, and after 5 minutes, the state before water was attached, that is, a white checkerboard pattern on a blue background, and the characters became invisible.
The above-mentioned aspect change can be repeated many times by adhering water, and is useful as an educational toy or a training toy.

Production of discolored body set Example 6
A discolored body set having excellent portability was obtained by combining the discolored body of Example 5 and a pen having a fiber pen body or the like at the tip as a means for adhering water and having a structure capable of accommodating water in a barrel. ..
When writing with the pen containing water in the white checkered pattern on the blue background of the discolored body, the characters "Japan" and "United States" appeared.
The above-mentioned aspect showed this state for 3 minutes in a room at 25 ° C. and 50% humidity, but as it dried, the porous layer and the porous image gradually became opaque, and the letters "Japan" and "United States" were visible. A white checkerboard pattern appeared, and after 5 minutes, the state before water was attached, that is, a white checkerboard pattern on a blue background, and the characters became invisible.
The above-mentioned aspect change can be repeated many times by adhering water, and is useful as an educational toy or a training toy.

Example 6
Preparation of discolored material Process printing (resolution: 180 lines, 350 dpi) on white synthetic paper as a support using non-discoloring UV curable offset printing inks of cyan, magenta, yellow, and black with an offset printing machine. A black colored image consisting of the 8-point characters "dog" and "cat" was formed.
Next, on each of the colored images, 15 parts of wet silicone (trade name: Nipseal E-200, manufactured by Nippon Silica Industry Co., Ltd.), pink pigment [trade name: TC Rubin FR-H, Dainichi Seika Kogyo (trade name: TC Rubin FR-H) Made by Co., Ltd.] 1.5 parts, Urethane emulsion [Product name: Hydran HW-930, Made by Dainippon Ink and Chemicals Co., Ltd., Solid content 50%] 30 parts, Water 40 parts, Silicone defoamer 0.5 Using a pink screen printing ink that is made by uniformly mixing and stirring parts, 3 parts of thickener for water-based ink, 1 part of ethylene glycol, and 1 part of isocyanate-based cross-linking agent, the entire surface is covered with a 100-mesh screen plate. It was solid-printed and dried and cured at 70 ° C. for 5 minutes to form a porous layer.
Next, on the porous layer, 12 parts of wet silicone (trade name: Nipseal E-200, manufactured by Nippon Silica Industry Co., Ltd.), urethane emulsion [trade name: Hydran HW-930, Dainippon Ink and Chemicals Co., Ltd.] ), Solid content 50%] 30 parts, 35 parts of water, 0.5 parts of silicone defoamer, 3 parts of thickener for water-based ink, 1 part of ethylene glycol, 1 part of isocyanate-based cross-linking agent are uniformly mixed. Using a white screen printing ink made by stirring, printing is performed on a screen plate with a polka dot pattern of 150 mesh, and the mixture is dried and cured at 70 ° C. for 5 minutes to form a porous image of a polka dot pattern. Got
The area ratio of the area where the porous layer was visually recognized in the dry state to the area where the porous image was visually recognized in the dry state was 30:70.
A picture of an animal (dog and cat) is printed on the support as a problem display part, and a overprint printing part of the colored image, the porous layer, and the porous image is provided in the vicinity of the picture of the dog and the cat. The colored image is the correct answer for the question display section.
The dry color density (D1) of the porous layer provided on the colored image is 1.36 (K: 0.59, C: 0.15, M: 0.45, Y: 0.17). The dry color density (D2) of the porous layer provided on the support is 0.55 (K: 0.18, C: 0.01, M: 0.30, Y: 0.06), porous. The dry color density (D3) of the porous image provided on the layer is 0.41 (K: 0.07, C: 0.03, M: 0.28, Y: 0.03), and D1. -D2 = 0.81 and D2-D3 = 0.14.

In the dry state, a porous image of white polka dots on a pink porous layer (white polka dots on a pink background) is visually recognized in the vicinity of the animal picture (dog and cat). However, when water is attached with a finger to which water is attached, the porous image becomes transparent and the porous layer becomes pink and transparent, so that the entire surface becomes pink and the porous layer becomes pink. The characters "dog" and "cat" appear in red and black, which is a mixture of the black color of the colored image.
The above-mentioned aspect showed this state for 3 minutes in a room at a temperature of 25 ° C. and a humidity of 50%, but as it dried, the porous layer and the porous image gradually became opaque, and the letters "dog" and "cat" were visible. As it became difficult to do so, a pattern of white polka dots appeared, and after 5 minutes, it became a state before water was attached, that is, a pattern of white polka dots on a pink background, and the characters became invisible.
The above-mentioned aspect change can be repeated many times by adhering water, and is useful as an educational toy or a training toy.

Production of discolored body set Example 7
A discolored body set having excellent portability was obtained by combining the discolored body of Example 6 with a pen having a fiber pen body or the like at the tip as a means for adhering water and having a structure capable of accommodating water in a barrel. ..
When writing with the pen containing water in the place where the white polka dots were drawn on the pink background of the discolored body, the characters "dog" and "cat" appeared.
The above-mentioned aspect showed this state for 3 minutes in a room at 25 ° C. and 50% humidity, but as it dried, the porous layer and the porous image gradually became opaque, and the letters "dog" and "cat" were visible. The pattern of white polka dots appeared, and after 5 minutes, the pattern before water was attached, that is, the pattern of white polka dots on a pink background, and the characters became invisible.
The above-mentioned aspect change can be repeated many times by adhering water, and is useful as an educational toy or a training toy.

Comparative Example 1
Preparation of discolored material Process printing (resolution: 180 lines, 350 dpi) on white synthetic paper as a support using non-discoloring UV curable offset printing inks of cyan, magenta, yellow, and black with an offset printing machine. A black colored image consisting of the 12-point character "Tokyo" and the character "Tokyo" consisting of the 6-point offset kana was formed in the upper part of the character.
Next, on the colored image, 15 parts of wet silicone (trade name: Nipseal E-200, manufactured by Nippon Silica Industry Co., Ltd.), blue pigment [trade name: Sundai Super Blue F707-E, manufactured by Sanyo Dye Co., Ltd.] ] 0.4 parts, urethane emulsion [Product name: Hydran HW-930, manufactured by Dainippon Ink and Chemicals Co., Ltd., solid content 50%] 30 parts, water 40 parts, silicone-based defoamer 0.5 parts, water-based Using a blue screen printing ink obtained by uniformly mixing and stirring 3 parts of thickener for ink, 1 part of ethylene glycol, and 1 part of isocyanate-based cross-linking agent, solid printing is performed on the entire surface with a 100-mesh screen plate. It was dried and cured at 70 ° C. for 5 minutes to form a porous layer.
Next, on the porous layer, 12 parts of wet silicone (trade name: Nipseal E-200, manufactured by Nippon Silica Industry Co., Ltd.), urethane emulsion [trade name: Hydran HW-930, Dainippon Ink and Chemicals Co., Ltd.] ), Solid content 50%] 30 parts, 35 parts of water, 0.5 parts of silicone defoamer, 3 parts of thickener for water-based ink, 1 part of ethylene glycol, 1 part of isocyanate-based cross-linking agent are uniformly mixed. Using a white screen printing ink made by stirring, printing was performed on a screen plate having a dot pattern of 150 mesh, and the mixture was dried and cured at 70 ° C. for 5 minutes to form a porous image of the dot pattern to obtain a discolored product. ..
The area ratio of the area where the porous layer was visually recognized in the dry state to the area where the porous image was visually recognized in the dry state was 90:10.
A map of Japan is printed on the support as a problem display unit, and an overprint printing unit of the colored image, the porous layer, and the porous image is provided in the vicinity of the position of Tokyo on the Japanese map, and the coloring is performed. The image is the correct answer for the question display.
In the dry state, the discolored body has a porous image of white dots (white dots on a blue background) on a pastel-like blue porous layer near Tokyo on a map of Japan, but a colored image. Because the effect of visually camouflaging is poor, the letters "Tokyo" can be visually recognized through the pale blue of the porous layer and the white dot pattern of the porous image, satisfying the practicality as an educational toy or a training toy. There wasn't.

Comparative Example 2
Preparation of discolored material Process printing (resolution: 180 lines, 350 dpi) on white synthetic paper as a support using non-discoloring UV curable offset printing inks of cyan, magenta, yellow, and black with an offset printing machine. A black colored image consisting of the 12-point character "Tokyo" and the character "Tokyo" consisting of the 6-point offset kana was formed in the upper part of the character.
Next, on the colored image 3, 15 parts of wet silicone (trade name: Nipseal E-200, manufactured by Nippon Silica Industry Co., Ltd.), blue pigment [trade name: Sundai Super Blue F707-E, Sanyo Dye Co., Ltd.] Manufactured by 0.4 parts, Urethane emulsion [Product name: Hydran HW-930, manufactured by Dainippon Ink and Chemicals Co., Ltd., solid content 50%] 30 parts, water 40 parts, silicone-based defoamer 0.5 parts, Solid printing is performed on the entire surface with a 100-mesh screen plate using a blue screen printing ink obtained by uniformly mixing and stirring 3 parts of a thickener for water-based ink, 1 part of ethylene glycol, and 1 part of an isocyanate-based cross-linking agent. , 70 ° C. was dried and cured for 5 minutes to form a porous layer.
Next, on the porous layer, 12 parts of wet silicone (trade name: Nipseal E-200, manufactured by Nippon Silica Industry Co., Ltd.), urethane emulsion [trade name: Hydran HW-930, Dainippon Ink and Chemicals Co., Ltd.] ), Solid content 50%] 30 parts, 35 parts of water, 0.5 parts of silicone defoamer, 3 parts of thickener for water-based ink, 1 part of ethylene glycol, 1 part of isocyanate-based cross-linking agent are uniformly mixed. Using a white screen printing ink made by stirring, print on a screen plate with a check pattern of 150 mesh, and dry and cure at 70 ° C. for 5 minutes to form a porous image of a dot pattern to form a discolored body. Obtained.
The area ratio of the area where the porous layer was visually recognized in the dry state to the area where the porous image was visually recognized in the dry state was 10:90.
A map of Japan is printed on the support as a problem display unit, and an overprint printing unit of the colored image, the porous layer, and the porous image is provided in the vicinity of the position of Tokyo on the Japanese map, and the coloring is performed. The image is the correct answer for the question display.
In the dry state, the discolored body has a porous image of white dots (white dots on a blue background) on a pastel-like blue porous layer near Tokyo on a map of Japan, but a colored image. Because the effect of visually camouflaging is poor, the letters "Tokyo" can be visually recognized through the pale blue of the porous layer and the white dot pattern of the porous image, satisfying the practicality as an educational toy or a training toy. There wasn't.

1 Discolored body 2 Support 3 Colored image 4 Porous layer 5 Porous image

Claims (10)

A colored image is formed on the support, and a low refractive index pigment and a coloring agent are fixed on the colored image together with a binder resin in a dispersed state. The colored image is opaque in a dry state to hide the colored image, and the colored image is colored and transparent in a liquid absorbing state. The low refractive index pigment is fixed together with the binder resin in a dispersed state on the porous layer in which the colored image is visually recognized, and the colored image is concealed and absorbed in a dry state. A porous image that is transparent in the liquid state to make the colored image visible is provided, and the area ratio of the portion where the porous layer is visible in the dry state to the area where the porous image is visible in the dry state. Is a discolored body in the range of 20:80 to 80:20. The discolored body according to claim 1, wherein the area ratio of the area where the porous layer is visible in the dry state to the area where the porous image is visible in the dry state is in the range of 30:70 to 70:30. .. The dry color density (D1) of the porous layer provided on the colored image, the dry color density (D2) of the porous layer provided on the support, and the porous state provided on the porous layer. The discolored body according to claim 1 or 2, wherein the color density (D3) in a dry state of the image satisfies the formulas (1) and (2).
0 ≦ D1-D2 <1.0 (1)
0 <D2-D3 (2) The discolored body according to any one of claims 1 to 3, wherein a problem display unit is provided around the porous layer, and the colored image is the correct answer of the problem display unit. The discolored body according to claim 4, further comprising a plurality of problem display units and a plurality of colored images. The discolored body according to claim 5, wherein the character size of the colored image is a character in the range of 3 to 13 points. The discolored body according to claim 6, wherein the colored image is a process print image. The discolored body according to any one of claims 4 to 7, wherein the problem display unit is a map and the colored image is a place name. The discolored body according to any one of claims 4 to 7, wherein the problem display unit is a national flag and the colored image is a country name. A color changer set comprising the color changer according to any one of claims 1 to 9 and a water adhering tool.

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