JP7341739B2 - Color change body, color change body set - Google Patents

Description

The present invention relates to a color change body and a color change body set. More specifically, it relates to a color changing body and a color change body set in which the hidden image is difficult to distinguish in a dry state, but the hidden image is clearly visible in a state where it absorbs a liquid such as water.

Conventionally, as a sheet that allows different images to be seen in dry and water-absorbed states, a coating layer containing a low refractive index pigment and a transparent film with a surface image on the coating layer are pasted onto a backing paper with an image on the colored surface. A water image sheet has been disclosed (for example, see Patent Document 1).
When the water image sheet is dry, the coating layer hides the image in the lower layer, so only the surface image is visible, and in the liquid absorbing state, the coating layer becomes transparent, and the surface image does not match the color tone of the mount or the image in the lower layer. It is configured so that only the image on the lower layer is visible, and even if a different image is visible, the surface image is made to be in sync with the color tone of the image on the lower layer and/or the mount. It is necessary to use similar colors or lighter colors, and to prevent the surface image and the underlying image from overlapping as much as possible. Therefore, it is difficult to visually recognize the image in the lower layer in a dry state, and it is not suitable for a structure in which the image is clearly visible in a liquid-absorbed state.

Japanese Unexamined Patent Publication No. 63-260476

The present invention aims to solve the problems of conventional water image sheets, namely, in a dry state, a hidden colored image is difficult to see, and in a liquid-absorbed state, the colored image is clearly visible. The purpose is to provide a color change body and a color change body set.

The present invention provides a colored image on a support, a low refractive index pigment and a coloring agent fixed on the colored image in a dispersed state together with a binder resin, the colored image is made opaque in a dry state, and the colored image is hidden, and the colored image is in a liquid-absorbing state. A porous layer that becomes colored and transparent to make the colored image visible; a low refractive index pigment is fixed in a dispersed state together with a binder resin on the porous layer where the colored image is provided, and the porous layer is made opaque in a dry state to make the colored image visible A porous image is provided that hides and becomes transparent in a liquid absorption state to make the colored image visible, and the area of the part where the porous layer is visible in a dry state and the porous image is visible in a dry state. The area ratio of the areas is in the range of 30:70 to 70:30 , and the dry color density (D1) of the porous layer provided on the colored image and the dry state of the porous layer provided on the support are The state color density (D2) and the dry state color density (D3) of the porous image provided on the porous layer satisfy equations (1) and (2), and a problem is displayed around the porous layer. , and the colored image is a color-changing object in which the correct answer of the question display section is required .
0≦D1-D2<0.5 (1)
0.1≦D2-D3 (2)
Furthermore , it comprises a plurality of problem display parts and a plurality of colored images, the font size of the colored images is in the range of 3 to 13 points, and the colored images are process printed images. The requirements include that the problem display part is a map, the colored image is a place name, and the problem display part is a national flag, and the colored image is the name of the country.
Furthermore, a color changing body set consisting of a color changing body and a water adhesion tool is required.

In the dry state, the hidden colored image is difficult to see, and in the liquid-absorbed state, the colored image is clearly visible, and the present invention has excellent applicability to various fields such as the toy field, decoration field, and design field. We can provide color change bodies and color change body sets.

FIG. 1 is an explanatory longitudinal cross-sectional view of an embodiment of a color changing body of the present invention.

The present invention is directed to a color-changing body that has different aspects visible when it is dry and when it has absorbed a liquid such as water, and whose appearance that is visible when it has absorbed liquid is difficult to distinguish when it is dry, and a color change body that uses the same. There is a color change body set, which will be explained below.

Any substrate suitable for printing may be used as the support, such as paper, synthetic paper, fabrics such as woven, knitted, plaited, and nonwoven fabrics, natural or synthetic leather, plastic, glass, ceramics, and metal. , wood, stone, etc. are used. Moreover, although a planar shape is preferable as the shape, an uneven shape may also be used.

A colored image is provided on the support.
The colored image is formed from a binder resin containing a coloring agent.
Examples of the coloring agent include general dyes, general pigments, fluorescent dyes, fluorescent pigments, metallic luster pigments, and the like.
The colorant forms a colored image by applying ink or paint contained in a vehicle containing a binder resin as a binder to a support, and then drying volatile components.
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 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 include resin emulsions, casein, starch, cellulose derivatives, polyvinyl alcohol, urea resins, phenol resins, and the like.
The colored image can be produced using printing methods such as process printing, screen printing, offset printing, gravure printing, coater, tampo printing, inkjet printing, transfer, etc., brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, and roller coating. , formed on a support by dip coating or the like.
In addition, a transfer layer is provided by applying ink or paint contained in a vehicle containing a colorant and a binder resin as a binder onto another base material in advance, and the transfer layer is transferred onto the support to form a colored image. It is also possible to provide
Note that the colored image can be made into a multicolored image by using a plurality of colorants of different colors, and since the colorful image can be visually recognized, it is also possible to improve the marketability.
Furthermore, when the support has transparency, a colored image may be provided on the back surface of the support (the surface on which the porous layer and porous image are not provided).
The colored image may include various letters, numbers, symbols, figures, many parallel lines, intersecting lines, a honeycomb shape, a grid shape, a grid shape, a tortoise shell pattern, and other geometric patterns formed by a combination of lines. , shapes of people, animals, plants, fruits, foodstuffs, vehicles, buildings, celestial bodies, etc.

The porous layer is a layer in which a low refractive index pigment and a colored image are fixed in a dispersed state together with a binder resin, and when dried, it becomes colored and opaque and hides the underlying layer, thereby preventing the colored image from being seen. Because of this, the porous image described below can be clearly seen.
The colorant may be the same as the colorant used for colored images.
Examples of the low refractive index pigments include silicic acid and its salts, barite powder, barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, talc, alumina white, magnesium carbonate, etc., and these have a refractive index of 1.4 to 1.4. It is in the range of 1.8 and shows good transparency when water is absorbed.
The silicic acid salts include aluminum silicate, potassium aluminum silicate, sodium aluminum silicate, calcium aluminum silicate, potassium silicate, calcium silicate, sodium calcium silicate, sodium silicate, magnesium silicate, potassium magnesium silicate, and the like.
Note that examples of low refractive index pigments that are suitably used include silicic acid and silicates.
Moreover, two or more kinds of the low refractive index pigments can also be used in combination.
The particle size of the low refractive index pigment is not particularly limited, but a particle size of 0.03 to 10.0 μm is preferably used.
The silicic acid may be produced by a dry process, but silicic acid produced by a wet process (hereinafter referred to as wet process silicic acid) is particularly effective. To explain this point, silicic acid is amorphous. It is produced as high-quality amorphous silicic acid, and depending on its production method, it is produced by a dry process using a gas phase reaction such as thermal decomposition of silicon halides such as silicon tetrachloride (hereinafter referred to as dry process silicic acid), and sodium silicate. The dry process silicic acid and the wet process silicic acid have different structures, and the dry process silicic acid has a three-dimensional structure in which silicic acid is tightly bonded. In contrast, wet process silicic acid has a so-called two-dimensional structural part in which silicic acid is condensed to form a long molecular arrangement.
Therefore, since the molecular structure is coarser compared to the dry process silicic acid, when wet process silicic acid is applied to a porous layer, it has excellent diffused reflection of light in a dry state compared to a system using dry process silicic acid, It is inferred that the concealability under normal conditions will be greater.
In addition, since the porous layer mainly absorbs water, wet-processed silicic acid has more hydroxyl groups present as silanol groups on the particle surface than dry-processed silicic acid, and has a higher degree of hydrophilicity. , is suitably used.
In addition, in order to adjust the concealing property of the porous layer in a normal state and the transparency in a liquid-absorbing state, other low refractive index pigments can be used in combination with wet process silicic acid.

The low refractive index pigment in the porous layer depends on the properties such as particle size, specific surface area, oil absorption amount, etc., but in order to satisfy both the hiding property in normal state and the transparency in liquid absorption state, The coating amount is preferably 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 power under normal conditions, and if it exceeds 30 g/m ² , it is difficult to obtain sufficient transparency during liquid absorption.
The low refractive index pigment and coloring agent are dispersed in a vehicle containing a binder resin as a binding agent, and after being coated on a support, volatile components are 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 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 include resin emulsions, casein, starch, cellulose derivatives, polyvinyl alcohol, 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 is preferably 0.5 to 2 parts by mass of the binder resin solids per 1 part by mass of the low refractive index pigment. parts, more preferably 0.8 to 1.5 parts by mass. If the binder resin solid content 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 if it exceeds 2 parts by mass. In this case, the permeability of water into the inside of the porous layer is likely to be impaired.
In the porous layer, since the mixing ratio of the binder resin to the colorant is smaller than that of a general coating film, it is difficult to obtain sufficient film strength. Therefore, in order to increase the scratch resistance, it is effective to use nylon resin or urethane resin among the binder resins mentioned above.
The urethane resins include polyester urethane resins, polycarbonate urethane resins, polyether urethane resins, etc., and two or more types can also be used in combination. In addition, urethane emulsion resins in which the resin is emulsified and dispersed in water, and colloids that are self-emulsified without the need for emulsifiers due to the ionic groups of the ionic urethane resin (urethane ionomer) and are dissolved or dispersed in water. Dispersion type (ionomer type) urethane resin can also be used.
The urethane resin may be either an aqueous urethane resin or an oil-based urethane resin, but aqueous urethane resins, particularly urethane emulsion resins and colloidal dispersion type urethane resins, are preferably used.
The urethane 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 a urethane resin is used in combination, in order to obtain practical film strength, it is preferable that the binder resin of the porous layer contains the urethane resin in a solid content mass ratio of 30% or more.
If the binder resin is crosslinkable, the film strength can be further improved by adding an arbitrary crosslinking agent to crosslink the binder resin.
The binder resins have different affinities with water, but by combining these binder resins, it is possible to adjust the time of penetration into the porous layer, the degree of penetration, and the slow rate of drying after penetration. Furthermore, the above adjustment can be controlled by appropriately adding a dispersant or a surfactant.

The porous layer can be formed by printing means such as screen printing, offset printing, gravure printing, coater, tampo printing, transfer, etc., brush coating, spray coating, electrostatic coating, electrodeposition coating, flow 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 in a dispersed state together with a binder resin, which becomes opaque in a dry state to hide the colored image, and becomes transparent in a liquid-absorbed state to form a colored image. A porous image is provided to make it visible.
In order to make the colored image clearly visible, it is conceivable to increase the density of the colored image and to reduce the amount of low refractive index pigment contained in the porous layer, but on the other hand, if the porous layer is in a dry state , it no longer shows sufficient concealment.
The porous image is an image in which a low refractive index pigment is fixed in a dispersed state together with a binder resin, and when it is dried, it becomes opaque and a white porous image is visible, and when it is dried, the porous layer is completely colored. Even if it is not hidden, it is possible to give the effect of visually concealing it. That is, the porous image partially hides the afterimage caused by the colored image (the colored image visible through the porous layer in a dry state), and visually camouflages the afterimage in areas where the porous image is not provided. have an effect.
The low refractive index pigment and binder resin may be the same as the low refractive index pigment and binder resin used in the porous layer.
The porous image can be formed by the same method as the porous layer.
In the color change body obtained as described above, in the liquid absorption state, the porous image becomes transparent and is no longer visible, and the porous layer also becomes colored and transparent, so that the colored image is visible. Note that the color of the colored image visually recognized in the liquid absorption state is a color mixed with the color of the porous layer.
Therefore, a porous image in a dry state and a colored image in a liquid-absorbed state can be viewed alternatively.

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 30:70 to 70:30 , more preferably 40:60 to 60. : In the range of 40.
By satisfying the above-mentioned area ratio, the porous image can partially hide the afterimage caused by the colored image, and can sufficiently exhibit the effect of visually camouflaging the afterimage.

Furthermore, the color density (D1) in a dry state of the porous layer provided on the colored image, the color density (D2) in a dry state of the porous layer provided on the support, and the color density (D2) in a dry state of the porous layer provided on the porous layer. It is preferable that the dry state color density (D3) of the porous image satisfies both formulas (1) and (2), and the color of the porous layer provided on the colored image and the porous layer provided on the support is Even if there is a difference in density as shown by formula (1), the dry state color density (D2) of the porous layer provided on the support and the dry state color density of the porous image provided on the porous layer When (D3) has the difference shown by formula (2), the effect of visually camouflaging the afterimage can be further expressed.
The formula (1) satisfies 0≦D1-D2<0.5, and the formula (2) satisfies 0.1≦D2-D3.
In addition, the dry state color density (D1) of the porous layer provided on the colored image, the dry state color density (D2) of the porous layer provided on the support, and the porous image provided on the porous layer. The dry state color density (D3) was the sum of the K value, C value, M value, and Y value of the density, which were each measured using a fluorescence spectrodensitometer FD-7 manufactured by Konica Minolta.

A question display part is provided around the porous layer of the color change body (around the overprinted part of the colored image, the porous layer, and the porous image), and the colored image is the correct answer of the question display part. It is possible to obtain a color-changing body suitable for use as an educational tool, an educational toy, a teaching tool, or a teaching toy.
In a system in which a question display section is provided around the porous layer, and the colored image is the correct answer of the question display section, by providing a plurality of question display sections and a plurality of colored images, it can be used for practical purposes in educational and educational purposes. It is possible to obtain a metachromatic material with rich properties.
The color-changing body with a plurality of problem display areas and a plurality of colored images has excellent ability to form a plurality of colored images by using characters whose size ranges from 4 to 12 points, and is highly educational. It is possible to obtain a color-changeable body that is highly practical for teaching purposes, and because the colored image is a process-printed image, the image has excellent clarity.
Specifically, the educational tool, educational toy, teaching tool, or educational toy includes a color changing object in which the problem display part is a map and the colored image is a place name; the problem display part is a national flag, and the colored image is a country name. One example is a color change body.

Specific embodiments of the color changing body include, for example, stuffed animals, dolls, doll costumes such as doll dresses, doll accessories such as bags, water gun targets, animal models, and human and doll handprints. Examples include toys such as boards that display traces such as footprints and footprints, teaching tools such as watercolor sheets, clothing such as dresses and swimsuits, shoes, bags, furniture, artificial flowers, and coasters.
It can also be applied as various indicators, such as detecting liquid leaks in piping, pipes, water tanks, tanks, etc., detecting water wetness of personal items and furniture, detecting water wetness in transportation and storage locations of water-resistant chemicals, and dew condensation. , detection of urine in disposable diapers, detection of moisture in soil, etc.

As a means for attaching water to the color-changing body, in addition to directly immersing it in water, moistening hands and fingers with water, and bringing it into contact, a water-applying tool can also be used.
The water application tools include a water gun, a sprayer, a writing or applicator having a brush tip or a fiber pen body, etc., a fibrous body or brush that stores water in a container and draws out the water from the container. Examples include writing or applicator tools, stamp tools, and the like.
A writing instrument or an applicator in which a plastic porous body or a processed fiber body having continuous pores is used as the nib member of the water adhesion tool can easily form a written image, and can improve practicality.
Note that a color-changing body set can also be configured by combining the water adhesion tool and a color-changing body.

Examples are shown below, but the present invention is not limited thereto.
In addition, parts in Examples indicate parts by mass.
Example 1 (see Figure 1)
Preparation of color-change body Process printing was performed on white synthetic paper as support 2 using an offset printing machine using cyan, magenta, yellow, and black non-color-changing UV-curable offset printing inks (resolution: 180 lines, 350 dpi) Then, a black colored image 3 consisting of 12-point characters "Tokyo" and characters "Tokyo-to" consisting of 6-point okurigana characters above the characters was formed.
Next, on the colored image 3, 15 parts of wet process silicic acid [trade name: Nip Seal E-200, manufactured by Nippon Silica Kogyo Co., Ltd.] and a blue pigment [trade name: Sandai Super Blue F707-E, manufactured by Sanyo Shiki Co., Ltd.] are added. [manufactured by] 0.4 part, urethane emulsion [trade name: Hydran HW-930, manufactured by Dainippon Ink & Chemicals Co., Ltd., solid content 50%] 30 parts, water 40 parts, silicone antifoaming agent 0.5 part, Using a blue screen printing ink made by uniformly mixing and stirring 3 parts of a water-based ink thickener, 1 part of ethylene glycol, and 1 part of an isocyanate-based crosslinking agent, solid printing was performed on the entire surface using a 100 mesh screen plate. The porous layer 4 was formed by drying and curing at 70° C. for 5 minutes.
Next, on the porous layer 4, 12 parts of wet process silicic acid [trade name: Nip Seal E-200, manufactured by Nippon Silica Kogyo Co., Ltd.] and urethane emulsion [trade name: Hydran HW-930, manufactured by Dainippon Ink and Chemicals Co., Ltd.] were applied. Co., Ltd., solid content 50%], 35 parts of water, 0.5 parts of silicone antifoaming agent, 3 parts of thickener for water-based ink, 1 part of ethylene glycol, and 1 part of isocyanate crosslinking agent were uniformly mixed. Using a stirred white screen printing ink, print on a screen plate with a 150 mesh dot pattern, dry and harden at 70°C for 5 minutes to form a porous image 5 with a dot pattern, and produce a color change body 1. I got it.
The area ratio of the area where the porous layer was visible in a dry state to the area where the porous image was visible in a dry state was 50:50.
A map of Japan is printed on the support as a question display area, and an overprinted area of the colored image, a porous layer, and the porous image is provided near the location of Tokyo on the map of Japan, and the colored image is overprinted with the porous image. The image is the correct answer on the question display section.
Further, the color density (D1) of the porous layer provided on the colored image shown in FIG. 1 in a dry state is 1.31 (K: 0.38, C: 0.64, M: 0.20 , Y: 0.09), and the dry color density (D2) of the porous layer provided on the support shown by B in FIG. 1 is 1.19 (K: 0.36, C: 0.64, M: 0.16, Y: 0.03), the color density (D3) in the dry state 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.

When the color-change body is dry, a porous image with a white dot pattern on a pastel blue porous layer (white dot pattern on a blue background) is visible on a pastel blue porous layer near Tokyo on the map of Japan, but when water is removed, When water is applied using a brush dipped in water, the porous image becomes transparent, and the porous layer also becomes blue and transparent, so the entire surface becomes blue, and the blue of the porous layer and the black of the colored image are mixed. The words ``Tokyo'' and ``Tokyo'' appeared in a dark blue color mixture.
The above appearance remained in this state for 3 minutes indoors at 25°C and 50% humidity, but as it dried, the porous layer and porous image gradually became opaque and the characters ``Tokyo'' and ``Tokyo'' appeared. became difficult to visually recognize, and a white dot pattern appeared, and after 5 minutes, it returned to the state before water was applied, that is, a white dot pattern on a blue background, and the letters were no longer visible.
The above change in appearance can be repeated many times by applying water to the toy, making it useful as an educational toy or a teaching toy.

Example 2
Preparation of color change body set A highly portable color change body was created by combining the color change body of Example 1 with a pen having a fiber pen body etc. at the tip as a water attachment means and configured to be able to accommodate water in the barrel. I got a body set.
When the pen filled with water was used to write on the white dot pattern on the blue background of the color change body, the words "Tokyo" and "Tokyo" appeared.
The above appearance remained in this state for 3 minutes indoors at 25°C and 50% humidity, but as it dried, the porous layer and porous image gradually became opaque and the characters ``Tokyo'' and ``Tokyo'' appeared. became difficult to visually recognize, and a white dot pattern appeared, and after 5 minutes, it returned to the state before water was applied, that is, a white dot pattern on a blue background, and the letters were no longer visible.
The above change in appearance can be repeated many times by applying water to the toy, making it useful as an educational toy or a teaching toy.

Example 3
Preparation of color-changing body Process printing (resolution: 180 lines, 350 dpi) was carried out using an offset printing machine using cyan, magenta, yellow, and black non-color-changing UV-curable offset printing inks on white synthetic paper as a support. A blue colored image consisting of the 7-point character "Nihon" and the 4-point okurikana character "Nihon" above the character was formed.
Next, on the colored image, 15 parts of wet process silicic acid [trade name: Nip Seal E-200, manufactured by Nippon Silica Kogyo Co., Ltd.], pink pigment [trade name: TC Rubin FR-H, Dainichiseika Kogyo Co., Ltd.] )] 1.0 part, urethane emulsion [trade name: Hydran HW-930, Dainippon Ink & Chemicals Co., Ltd., solid content 50%] 30 parts, water 40 parts, silicone antifoaming agent 0.5 part , 3 parts of a water-based ink thickener, 1 part of ethylene glycol, and 1 part of an isocyanate-based crosslinking agent were uniformly mixed and stirred to form a pink screen printing ink. It was printed and dried and cured at 70° C. for 5 minutes to form a porous layer.
Next, 12 parts of wet process silicic acid [trade name: Nip Seal E-200, manufactured by Nippon Silica Kogyo Co., Ltd.] and urethane emulsion [trade name: Hydran HW-930, manufactured by Dainippon Ink and Chemicals Co., Ltd.] were placed on the porous layer. ), solid content 50%], 35 parts of water, 0.5 parts of silicone antifoaming agent, 3 parts of thickener for water-based ink, 1 part of ethylene glycol, and 1 part of isocyanate crosslinking agent were uniformly mixed. Using a stirred white screen printing ink, it was printed on a screen plate with a 150 mesh polka dot pattern, and dried and cured at 70°C for 5 minutes to form a porous image with a polka dot pattern to obtain a color change body. .
The area ratio of the area where the porous layer was visible in a dry state to the area where the porous image was visible in a dry state was 70:30.
A Japanese national flag is printed on the support as a problem display area, and an overprinted area of the colored image, a porous layer, and a porous image is provided near the Japanese flag, and the colored image is a problem display area. The correct answer is displayed on the display.
Further, the color density (D1) of the porous layer provided on the colored image in a dry state is 0.78 (K: 0.23, C: 0.14, M: 0.30, Y: 0.11) , the dry state 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 texture 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 dry conditions, a porous image of white polka dots on a pastel pink porous layer is visible near the Japanese flag (white polka dots on a pink background); When you apply water with your finger, the porous image becomes transparent, and the porous layer becomes pink and transparent, so the entire surface becomes pink, and the pink color of the porous layer and the blue color of the colored image become transparent. The words ``Japan'' and ``Tokyo'' made up of mixed purple characters appeared.
The above condition remained in this state for 3 minutes in a room with a temperature of 25 degrees Celsius and a humidity of 50%, but as it dried, the porous layer and porous image gradually became opaque and changed from the original Japanese characters for "Japan" and "Nihon". The characters became difficult to see and a white polka dot pattern appeared, and after 5 minutes, the state before water was applied, that is, a white polka dot pattern on a pink background, and the characters ``Japan'' and ``Nihon'' appeared. Characters consisting of kana are no longer visible.
The above change in appearance can be repeated many times by applying water to the toy, making it useful as an educational toy or a teaching toy.

Example 4
Preparation of color change body set A highly portable color change body was created by combining the color change body of Example 3 with a pen having a fiber pen body etc. at the tip as a water attachment means and configured to be able to accommodate water in the barrel. I got a body set.
When the pen filled with water was used to write on the white polka dot pattern on the pink background of the color change body, the words "Japan" and "Nihon" appeared.
The above appearance remained in this state for 3 minutes indoors at 25°C and 50% humidity, but as it dried, the porous layer and porous image gradually became opaque, and the words "Japan" and "Nihon" were no longer visible. 5 minutes later, it became the state before water was applied, that is, a white polka dot pattern on a pink background, and the letters were no longer visible.
The above change in appearance can be repeated many times by applying water to the toy, making it useful as an educational toy or a teaching toy.

Example 5
Preparation of color-changing body Process printing (resolution: 180 lines, 350 dpi) was carried out using an offset printing machine using cyan, magenta, yellow, and black non-color-changing UV-curable offset printing inks on white synthetic paper as a support. Then, black colored images consisting of 6-point characters "Japan" and "United States of America" were formed.
Next, 15 parts of wet process silicic acid [trade name: Nip Seal E-200, manufactured by Nippon Silica Kogyo Co., Ltd.] and a blue pigment [trade name: Sandai Super Blue F707-E, manufactured by Sanyo Shiki Co., Ltd.] were then applied onto each of the colored images. [manufactured by] 0.3 parts, urethane emulsion [trade name: Hydran HW-930, manufactured by Dainippon Ink & Chemicals Co., Ltd., solid content 50%] 30 parts, water 40 parts, silicone antifoaming agent 0.5 parts, Using a blue screen printing ink made by uniformly mixing and stirring 3 parts of a water-based ink thickener, 1 part of ethylene glycol, and 1 part of an isocyanate-based crosslinking agent, solid printing was performed on the entire surface using a 100 mesh screen plate. The porous layer was formed by drying and curing at 70° C. for 5 minutes.
Next, 12 parts of wet process silicic acid [trade name: Nip Seal E-200, manufactured by Nippon Silica Kogyo Co., Ltd.] and urethane emulsion [trade name: Hydran HW-930, manufactured by Dainippon Ink and Chemicals Co., Ltd.] were placed on the porous layer. ), solid content 50%], 35 parts of water, 0.5 parts of silicone antifoaming agent, 3 parts of thickener for water-based ink, 1 part of ethylene glycol, and 1 part of isocyanate crosslinking agent were uniformly mixed. Using stirred white screen printing ink, print on a screen plate with a 150 mesh check pattern, dry and harden at 70°C for 5 minutes to form a porous image with a checkered pattern to obtain a color change body. Ta.
The area ratio of the area where the porous layer was visible in a dry state to the area where the porous image was visible in a dry state was 80:20.
A world map is printed on the support as a problem display area, and an overprinted area of the colored image, porous layer, and porous image is provided near the locations of Japan and the United States of America on the world map, and The colored image is the correct answer on the question display section.
The color density (D1) of the porous layer provided on the colored image in a dry state is 1.26 (K: 0.38, C: 0.59, M: 0.20, Y: 0.09). , the dry state 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 texture 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, a porous image with a white lattice pattern on a pastel blue porous layer (white lattice pattern on a blue background) is visible on the world map near Japan and the United States; When water is applied using a brush soaked in water, the porous image becomes transparent, and the porous layer becomes blue and transparent, so the entire surface becomes blue, and the blue of the porous layer and the black of the colored image become transparent. The words ``Japan'' and ``United States of America'' appeared in dark blue with a mixture of colors.
The above appearance remained in this state for 3 minutes indoors at 25°C and 50% humidity, but as it dried, the porous layer and porous image gradually became opaque, and the words "Japan" and "United States of America" were no longer visible. 5 minutes later, it became the state before water was applied, that is, a white checkered pattern on a blue background, and the letters were no longer visible.
The above change in appearance can be repeated many times by applying water to the toy, making it useful as an educational toy or a teaching toy.

Preparation of color change body set Example 6
A highly portable color changing body set was obtained by combining the color changing body of Example 5 with a pen having a fiber pen body or the like at the tip as a water attachment means and configured to be able to store water in the barrel. .
When the pen filled with water was used to write on the white checkered pattern on the blue background of the color change body, the words "Japan" and "United States of America" appeared.
The above appearance remained in this state for 3 minutes indoors at 25°C and 50% humidity, but as it dried, the porous layer and porous image gradually became opaque, and the words "Japan" and "United States of America" were no longer visible. 5 minutes later, it became the state before water was applied, that is, a white checkered pattern on a blue background, and the letters were no longer visible.
The above change in appearance can be repeated many times by applying water to the toy, making it useful as an educational toy or a teaching toy.

Reference example 1
Preparation of color-changing body Process printing (resolution: 180 lines, 350 dpi) was carried out using an offset printing machine using cyan, magenta, yellow, and black non-color-changing UV-curable offset printing inks on white synthetic paper as a support. A black colored image consisting of 8-point characters ``dog'' and ``cat'' was formed.
Next, 15 parts of wet process silicic acid [trade name: Nip Seal E-200, manufactured by Nippon Silica Kogyo Co., Ltd.] and pink pigment [trade name: TC Rubin FR-H, Dainichiseika Kogyo Co., Ltd.] were added onto each of the colored images. Co., Ltd.] 1.5 parts, urethane emulsion [trade name: Hydran HW-930, Dainippon Ink & Chemicals Co., Ltd., solid content 50%] 30 parts, water 40 parts, silicone antifoaming agent 0.5 Using a pink screen printing ink made by uniformly mixing and stirring 1 part of water-based ink thickener, 1 part of ethylene glycol, and 1 part of isocyanate-based crosslinking agent, the whole surface was printed on a 100-mesh screen plate. A porous layer was formed by solid printing and drying and curing at 70° C. for 5 minutes.
Next, 12 parts of wet process silicic acid [trade name: Nip Seal E-200, manufactured by Nippon Silica Kogyo Co., Ltd.] and urethane emulsion [trade name: Hydran HW-930, manufactured by Dainippon Ink and Chemicals Co., Ltd.] were placed on the porous layer. ), solid content 50%], 35 parts of water, 0.5 parts of silicone antifoaming agent, 3 parts of thickener for water-based ink, 1 part of ethylene glycol, and 1 part of isocyanate crosslinking agent were uniformly mixed. Using stirred white screen printing ink, print on a screen plate with a 150-mesh polka dot pattern, dry and harden at 70°C for 5 minutes to form a porous image with a polka dot pattern, and create a color change object. I got it.
The area ratio of the area where the porous layer was visible in a dry state to the area where the porous image was visible in a dry state was 30:70.
Pictures of animals (a dog and a cat) are printed on the support as a problem display part, and an overprinted part of the colored image, a porous layer, and a porous image is provided near the picture of the dog and cat. The colored image is the correct answer on the question display section.
The color density (D1) of the porous layer provided on the colored image in a dry state is 1.36 (K: 0.59, C: 0.15, M: 0.45, Y: 0.17). , the dry state 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 texture 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.

When the color-change material is dry, a porous image of a cut-out pattern of white polka dots on a pink porous layer (a cut-out pattern of white polka dots on a pink background) is visible near a picture of an animal (dog and cat). However, if you apply water with your finger, the porous image becomes transparent and the porous layer becomes transparent in pink color. The words ``dog'' and ``cat'' appeared in red and black, which was a mixture of the black color of the colored image.
The above condition remained in this state for 3 minutes indoors at a temperature of 25°C and a humidity of 50%, but as it dried, the porous layer and porous image gradually became opaque, and the words "dog" and "cat" were no longer visible. As it became more difficult to see, a cut-out pattern of white polka dots appeared, and after 5 minutes, it became the state before water was applied, that is, a cut-out pattern of white polka dots on a pink background, and the letters were no longer visible.
The above change in appearance can be repeated many times by applying water to the toy, making it useful as an educational toy or a teaching toy.

Preparation of color change body set
Reference example 2
A color-changing body set with excellent portability was obtained by combining the color-changing body of Reference Example 1 with a pen having a fiber pen body etc. at the tip as a water attachment means and configured to be able to store water in the barrel. .
When the pen filled with water was used to write on the cutout pattern of white polka dots on the pink background of the color change body, the words "dog" and "cat" appeared.
The above appearance remained in this state for 3 minutes indoors at 25°C and 50% humidity, but as it dried, the porous layer and porous image gradually became opaque, and the words "dog" and "cat" were no longer visible. As it became more difficult to see, a cut-out pattern of white polka dots appeared, and after 5 minutes, it became the state before water was applied, that is, a cut-out pattern of white polka dots on a pink background, and the letters were no longer visible.
The above change in appearance can be repeated many times by applying water to the toy, making it useful as an educational toy or a teaching toy.

Comparative example 1
Preparation of color-changing body Process printing (resolution: 180 lines, 350 dpi) was carried out using an offset printing machine using cyan, magenta, yellow, and black non-color-changing UV-curable offset printing inks on white synthetic paper as a support. Then, a black colored image was formed consisting of 12-point characters "Tokyo" and the characters "Tokyo-to" consisting of 6-point okurigana characters above the characters.
Next, 15 parts of wet process silicic acid [trade name: Nip Seal E-200, manufactured by Nippon Silica Kogyo Co., Ltd.] and a blue pigment [trade name: Sandai Super Blue F707-E, manufactured by Sanyo Shiki Co., Ltd.] were added onto the colored image. ] 0.4 parts, urethane emulsion [trade name: Hydran HW-930, manufactured by Dainippon Ink and Chemicals Co., Ltd., solid content 50%] 30 parts, water 40 parts, silicone antifoaming agent 0.5 parts, water-based Using a blue screen printing ink made by uniformly mixing and stirring 3 parts of an ink thickener, 1 part of ethylene glycol, and 1 part of an isocyanate crosslinking agent, solid printing was performed on the entire surface with a 100 mesh screen plate, A porous layer was formed by drying and curing at 70° C. for 5 minutes.
Next, 12 parts of wet process silicic acid [trade name: Nip Seal E-200, manufactured by Nippon Silica Kogyo Co., Ltd.] and urethane emulsion [trade name: Hydran HW-930, manufactured by Dainippon Ink and Chemicals Co., Ltd.] were placed on the porous layer. ), solid content 50%], 35 parts of water, 0.5 parts of silicone antifoaming agent, 3 parts of thickener for water-based ink, 1 part of ethylene glycol, and 1 part of isocyanate crosslinking agent were uniformly mixed. Using a stirred white screen printing ink, printing was performed on a screen plate with a 150 mesh dot pattern, and the material was dried and cured at 70°C for 5 minutes to form a porous image with a dot pattern to obtain a color change body. .
The area ratio of the area where the porous layer was visible in a dry state to the area where the porous image was visible in a dry state was 90:10.
A map of Japan is printed on the support as a question display area, and an overprinted area of the colored image, a porous layer, and the porous image is provided near the location of Tokyo on the map of Japan, and the colored image is overprinted with the porous image. The image is the correct answer on the question display section.
In the dry state, a porous image of a white dot pattern on a pastel blue porous layer (a white dot pattern on a blue background) is visible on a pastel blue porous layer near Tokyo on the map of Japan, but the color change body is not a colored image. Because the visual camouflage effect is poor, the letters ``Tokyo'' can be seen through the pale blue color of the porous layer and the white dot pattern of the porous image, making it unsuitable for practical use as an educational toy or teaching toy. There wasn't.

Comparative example 2
Preparation of color-changing body Process printing (resolution: 180 lines, 350 dpi) was carried out using an offset printing machine using cyan, magenta, yellow, and black non-color-changing UV-curable offset printing inks on white synthetic paper as a support. Then, a black colored image was formed consisting of 12-point characters "Tokyo" and the characters "Tokyo-to" consisting of 6-point okurigana characters above the characters.
Next, on the colored image 3, 15 parts of wet process silicic acid [trade name: Nip Seal E-200, manufactured by Nippon Silica Kogyo Co., Ltd.] and a blue pigment [trade name: Sandai Super Blue F707-E, manufactured by Sanyo Shiki Co., Ltd.] are added. [manufactured by] 0.4 part, urethane emulsion [trade name: Hydran HW-930, manufactured by Dainippon Ink & Chemicals Co., Ltd., solid content 50%] 30 parts, water 40 parts, silicone antifoaming agent 0.5 part, Using a blue screen printing ink made by uniformly mixing and stirring 3 parts of a water-based ink thickener, 1 part of ethylene glycol, and 1 part of an isocyanate-based crosslinking agent, solid printing was performed on the entire surface using a 100 mesh screen plate. The porous layer was formed by drying and curing at 70° C. for 5 minutes.
Next, 12 parts of wet process silicic acid [trade name: Nip Seal E-200, manufactured by Nippon Silica Kogyo Co., Ltd.] and urethane emulsion [trade name: Hydran HW-930, manufactured by Dainippon Ink and Chemicals Co., Ltd.] were placed on the porous layer. ), solid content 50%], 35 parts of water, 0.5 parts of silicone antifoaming agent, 3 parts of thickener for water-based ink, 1 part of ethylene glycol, and 1 part of isocyanate crosslinking agent were uniformly mixed. Using stirred white screen printing ink, print on a screen plate with a 150 mesh check pattern, dry and harden at 70°C for 5 minutes to form a porous image with a cutout pattern of dots, and create a color change body. Obtained.
The area ratio of the area where the porous layer was visible in a dry state to the area where the porous image was visible in a dry state was 10:90.
A map of Japan is printed on the support as a question display area, and an overprinted area of the colored image, a porous layer, and the porous image is provided near the location of Tokyo on the map of Japan, and the colored image is overprinted with the porous image. The image is the correct answer on the question display section.
In the dry state, a porous image of a white dot pattern on a pastel blue porous layer (a white dot pattern on a blue background) is visible on a pastel blue porous layer near Tokyo on the map of Japan, but the color change body is not a colored image. Because the visual camouflage effect is poor, the letters ``Tokyo'' can be seen through the pale blue color of the porous layer and the white dot pattern of the porous image, making it unsuitable for practical use as an educational toy or teaching toy. There wasn't.

1 Color change body 2 Support body 3 Colored image 4 Porous layer 5 Porous image

Claims (7)

A colored image is formed on a support, and a low refractive index pigment and a coloring agent are fixed on the colored image in a dispersed state together with a binder resin.The colored image is made opaque in a dry state to hide the colored image, and the colored image is made transparent in a liquid-absorbed state. A porous layer that allows the colored image to be visually recognized; a low refractive index pigment is fixed in a dispersed state with a binder resin on the porous layer where the colored image is provided; it becomes opaque in a dry state and hides the colored image; A porous image that becomes transparent in a liquid state to make a colored image visible is provided, and the area ratio of the area where the porous layer is visible in a dry state to the area where the porous image is visible in a dry state. is in the range of 30:70 to 70:30 , and the dry state color density (D1) of the porous layer provided on the colored image and the dry state color density of the porous layer provided on the support (D2) and the dry state color density (D3) of the porous image provided on the porous layer satisfy formulas (1) and (2), and a problem display part is provided around the porous layer. , and the colored image is the correct answer on the question display section .
0≦D1-D2<0.5 (1)
0.1≦D2-D3 (2) The color changing body according to claim 1, comprising a plurality of problem display areas and a plurality of colored images. The color change body according to claim 2, wherein the color image has a character size in the range of 3 to 13 points. The color-changing body according to claim 3, wherein the colored image is a process printed image. 5. The color changing body according to claim 2, wherein the problem display section is a map, and the colored image is a place name. 5. The color-changing body according to claim 2, wherein the question display section is a national flag and the colored image is a country name. A color change body set comprising the color change body according to any one of claims 1 to 6 and a water adhesion tool.

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