JP2001051585A - Discolorable drawing for coloring and discolorable drawing set for coloring using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a discolorable drawing for coloring which is repetitively usable, is free of contamination by writing implements used for coloration and has excellent ease of convenience by making a non-discolorable image visible by the clarification or opacification of a porous layer in a water absorption state. SOLUTION: The surface of a base 2 is provided with the non-discolorable image 2 and part on the non-discolorable image 2 is provided with the porous layer 5. The porous layer 5 turns transparent or opaque by absorbing the water and makes the lower layer thereof visible. When the porous layer 5 of the portion where the water is absorbed dries, the porous layer 5 restores the original state and, therefore, this drawing for coloring allows the practicability of repetitive use. The porous layer 5 disposed on the non-discolorable image 2 is a layer formed by fixing low-refractive index pigments together with a binder resin in a dispersed state. The low-refractive index pigments include particulate silicic acid, barytes, low settling barium sulfate, barium carbonate, etc. The material of the base 3 is not particularly restricted and include synthetic paper, films, plastics, rubber, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a discolorable coloring book and a discolorable coloring set using the same. More specifically, the present invention relates to a coloring book that changes color by application of water, and a discoloration coloring book set including a discoloration tool that applies water and the discoloration coloring book.

[0002]

2. Description of the Related Art Conventionally, a coloring book in which an outline image is printed on a support such as paper has been widely used, and the coloring book is colored using a colored pencil or a crayon along the outline image.

[0003]

Since the above-mentioned conventional coloring book uses a general writing instrument, it tends to stain hands and clothes when applied, and also tends to stain the floor and the table supporting the coloring book. In addition, a coloring book that has been used once cannot be reused, and the user needs an unused coloring book, which is troublesome and costly.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a discolorable coloring book which can be used repeatedly, is free from contamination by a writing implement used for coloring and is excellent in convenience, and a discolorable coloring set using the same. That is, a non-color-change image is provided on a support, and a porous layer in which a low-refractive-index pigment is fixed in a dispersed state together with a binder resin on at least a part of the non-color-change image is provided. Discolorable coloring book that can be made transparent or translucent in a water-absorbing state to make a non-discolorable image visible, or
A porous layer in which a low refractive index pigment is fixed in a dispersed state together with a binder resin is provided on a support, and a non-discoloring contour image is provided on the porous layer. The porous layer is transparent or translucent in a water-absorbing state. Discoloration coloring book, which can be visualized and the color tone of the lower layer can be visualized, or a non-color-change image and a porous image in which a low refractive index pigment is fixed in a dispersed state together with a binder resin on a support side by side, and the porous layer absorbs water. A requirement is a discolorable coloring book that is transparent or translucent in the state and allows the color tone of the lower layer to be seen. Furthermore,
A discoloring coloring book set including a discoloring device to which water is applied and the discoloring coloring book is required.

[0005] The present invention is a coloring book in which water is adhered to a porous layer, water is permeated into the porous layer at that location to make the layer transparent or translucent, and images of different colors are visually recognized. It returns to its original state if the infiltrated water evaporates. The medium for discoloring the coloring book, water is preferably used in terms of simplicity, safety and cost, but propylene glycol or the like to adjust the drying speed and extend the visible time of the image,
A trace amount of a water-soluble organic solvent may be blended.

[0006] The discolorable coloring book of the present invention has a structure in which a non-discolorable image is provided on a support, and a porous layer is provided on at least a part of the non-discolorable image, and a porous layer is provided on the support. A configuration in which a non-color-change contour image is provided on the porous layer, or a configuration in which a non-color-change image and a porous image in which a low-refractive-index pigment is fixed in a dispersed state together with a binder resin on a support are arranged side by side. The porous layer absorbs water, becomes transparent or translucent, makes the lower layer visible, and returns to its original state when the porous layer in the portion that has absorbed water dries, so that repeated practical use is possible. Coloring book. The material of the support is not particularly limited as long as it has water resistance, and examples thereof include synthetic paper, cloth, film, plastic, rubber, synthetic leather, leather, glass, ceramics, wood, and stone. Further, even a material having poor water resistance, for example, high-quality paper, art paper, coated paper, etc., can be used as a support by a method such as lamination with a film, coating or impregnating a resin. The support is preferably in the form of a plane, but may be in the form of irregularities.

A description will be given of a structure in which a non-color-changeable image is provided on the above-described support and a porous layer is provided on at least a part of the non-color-changeable image. The non-color-changeable image is a portion corresponding to a pattern of a coloring book. And is formed of a non-color-changing ink containing a general dye or pigment, a fluorescent dye or pigment. The non-color-changeable image can be composed of a single color, but a multicolor image formed using non-color-changeable inks having different color tones is preferable.
Further, it is preferable that the non-discolorable image and the porous layer have different color tones.

The porous layer provided on the non-discolorable image is a layer in which a low refractive index pigment is fixed in a dispersed state together with a binder resin. Examples of the low-refractive-index pigment include particulate silica, barite powder, precipitated barium sulfate, barium carbonate, precipitated calcium carbonate, gypsum, clay, talc, alumina white, basic magnesium carbonate, and the like. Is in the range of 1.4 to 1.7, and shows good transparency when absorbing water. The particle size of the low refractive index pigment is not particularly limited, but may be in the range of 0.1 to 0.1.
Those having a size of from 03 to 10.0 μm are preferably used. Further, two or more low refractive index pigments may be used in combination.
In addition, as the low-refractive-index pigment that is preferably used, fine-particle silica can be used. Fine-particle silicic acid is produced as an amorphous amorphous silicic acid, and is produced by a dry method using a gas phase reaction such as thermal decomposition of silicon halide such as silicon tetrachloride (hereinafter referred to as a dry-method silicic acid). )
The method is roughly classified into a wet method using a liquid phase reaction such as decomposition with an acid such as sodium silicate (hereinafter referred to as a wet method particulate silica), and any of them can be used. When using silicic acid, the opacity in the normal state is greater than that of the dry method particulate silica, so it is possible to increase the mixing ratio of the binder resin to the particulate silica and improve the film strength of the porous layer. Therefore, it is more preferably used. As described above, the particulate silicic acid used for satisfying the concealability of the porous layer in the normal state is preferably a wet method particulate silica. This is because the dry process particulate silica and the wet process particulate silica have different structures, whereas the dry process particulate silica forms a three-dimensional structure in which silicic acid is tightly coupled as shown below. ,

[0009]

Embedded image

As described below, wet-process fine-particle silicic acid is formed by condensing silicic acid to form a long molecular arrangement.
It has a two-dimensional structural part. Therefore, since the molecular structure becomes coarser than that of the dry method particulate silica, when the wet method particulate silica is applied to the porous layer, the light in a dry state is lower than the system using the dry method particulate silica. It is presumed that it has excellent irregular reflection properties, and thus has a large concealing property under normal conditions.

[0011]

Embedded image

The low-refractive-index pigment contained in the porous layer desirably has an appropriate hydrophilicity because the medium that penetrates is mainly water, and the wet-process fine-particle silica is dry-process fine-particle. Since there are more hydroxyl groups present as silanol groups on the particle surface than in silicic acid, they have high hydrophilicity and are preferably used.

When the wet process particulate silica is used as a low refractive index pigment, the type, particle size,
Specific surface area, will depend on the nature of the oil absorption, etc., in order to satisfy both the transparency in the hiding properties and water absorption state at normal, it can coating amount is 1g / m ² ~30g / m ² preferably, more preferably ^{5g / m 2 ~20g / m 2} . If it is less than 1 g / m ² , it is difficult to obtain sufficient hiding properties under normal conditions, and if it exceeds 30 g / m ² , it is difficult to obtain sufficient transparency when absorbing water.

The low-refractive-index pigment is dispersed in a vehicle containing a binder resin as a binder, applied to a support, and then dried to form a porous layer by drying volatile components. As the binder resin, urethane resin, nylon resin, vinyl acetate resin, acrylate resin, acrylate copolymer resin, acrylic polyol resin, vinyl chloride-vinyl acetate copolymer resin, maleic acid resin, polyester resin, styrene Resin, styrene copolymer resin,
Polyethylene resin, polycarbonate resin, epoxy resin, styrene-butadiene copolymer resin, acrylonitrile-butadiene copolymer resin, methyl methacrylate-butadiene copolymer resin, butadiene resin, chloroprene resin, melamine resin, and the above resin emulsions, casein, starch , Cellulose derivatives, polyvinyl alcohol, urea resins, phenolic resins, epoxy resins and the like.

Since the mixing ratio of the binder resin to the colorant in the porous layer is smaller than that of a conventionally known general coating film, it is difficult to obtain a sufficient film strength. Therefore, in applications where washing resistance and scratch resistance are required,
It is preferable to use a urethane resin or a nylon resin as the above-mentioned binder resin, or to contain at least the resin. Examples of the urethane-based resin include a polyester-based urethane resin, a polycarbonate-based urethane resin, and a polyether-based urethane resin, and two or more kinds may be used in combination. In addition, a urethane emulsion resin in which the resin is emulsified and dispersed in water, or a colloid dissolved or dispersed in water by self-emulsifying without an emulsifier by an ionic group of a urethane resin having an ionic property (urethane ionomer) itself. Dispersion type (ionomer type)
Urethane resins can also be used. The urethane-based resin may be any of an aqueous urethane-based resin or an oil-based urethane-based resin.
In particular, urethane-based emulsion resins and colloid-dispersed urethane-based resins are preferably used. The urethane-based resin can be used alone, but may be used in combination with another binder resin depending on the type of the support and the performance required for the film. When using a binder resin other than a urethane-based resin, in order to obtain a practical film strength,
It is preferable that the binder resin of the porous layer contains a urethane resin at a solid content ratio of 30% or more.
In the binder resin, the crosslinking strength can be further improved by adding an optional crosslinking agent and crosslinking the binder resin. In the binder resin,
Depending on the degree of affinity with the medium, by combining these, it is possible to adjust the permeation time into the porous layer, the degree of permeation into the porous layer, and the speed of drying after permeation. Further, the above-mentioned permeation performance can be controlled by appropriately adding a dispersant.

Further, in the porous layer, conventionally known titanium dioxide-coated mica, iron oxide-titanium dioxide-coated mica, iron oxide-coated mica, guanine, sericite, basic lead carbonate, lead acid arsenate, oxyacid The color change can be varied by adding a metallic luster pigment such as bismuth chloride or adding a general dye or pigment.

The non-discolorable image and the porous layer are formed by a conventionally known method, for example, screen printing, offset printing,
It can be formed by printing means such as gravure printing, coater, tampo printing, transfer and the like, brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, dip coating and the like.

The above-mentioned porous layer has a constitution in which the non-discolorable image is partially concealed, and a coloring book in which water is adhered to the concealed portion may be mentioned. In this case, it is preferable that the porous layer is a porous image corresponding to the outline and contour of the non-color-changeable image. Further, the configuration may be such that the entire non-color-change image is concealed. However, in order to identify the position to be painted for practical use by specifying the coloring book, in the case of a configuration in which the porous layer covers the entire non-discolorable image, the porous layer is so porous that the lower non-discolorable image is slightly visible in a dry state. It is preferable to provide a layer so that a user can specify a portion to be coated.

Next, a configuration in which a porous layer is provided on a support and a non-color-changeable contour image is provided on the porous layer will be described. It is printed with a water-based ink, and is made transparent by adhering water to the porous layer in the outline to make it water-absorbing, so that the color tone of the lower layer can be visually recognized. Therefore, it is preferable that the support and the porous layer have different color tones, or a non-color-changing layer or a non-color-changing image having a different color from the porous layer is provided between the support and the porous layer. With the configuration in which the non-color-changeable contour image is provided, the work of painting a predetermined position is easy when coloring, and it is simple and convenient.

Further, a configuration in which a non-color-change image and a porous image in which a low-refractive index pigment is fixed in a dispersed state together with a binder resin on a support will be described. The water is absorbed by attaching water to the porous image. By making it in a state, it becomes transparent and the color tone of the support is visually recognized. Therefore, the colorless image and the porous image arranged side by side have different colors from each other,
It is preferable that the support and the porous image have different color tones, or that a non-color-changing layer or a non-color-changing colored image having a different color from the porous layer is provided between the support and the porous layer.

Discoloration coloring book formed as described above
If necessary, titanium dioxide-coated mica, iron oxide
Titanium oxide coated mica, iron oxide coated mica, guanine, cirrus
Mother, basic lead carbonate, lead acid arsenate, bismuth oxychloride, etc.
A metallic luster layer by applying an ink containing a metallic luster pigment
Reversible thermochromicity that reversibly discolors due to heat or temperature change
Providing a thermochromic layer containing the composition, or
By including the reversible thermochromic composition in the layer,
Adds a change in appearance due to heat or cold with a change in appearance due to the body
Can also be given. As the reversible thermochromic composition
Is, for example, (a) an electron-donating color-forming organic compound,
(B) an electron-accepting compound, and (c) a coloration of the two.
Contains three components of an organic compound medium that reversibly initiates the reaction.
Reversible thermochromic composition, liquid crystal, Ag_Two HgI _Four , Cu_Two 
HgI_Four Are used. The electron-donating color-forming organic compound
Reversible color reaction between the compound and the electron accepting compound
Reversible thermochromic composition containing three components of an organic compound medium
Specifically, specifically, JP-B-51-35414,
JP-B-51-44706, JP-B-51-4747
08, JP-B-52-7774, JP-B-1-
29398, JP-A-7-186546, etc.
What is described is mentioned. The above is the predetermined temperature (discoloration point)
The color changes before and after the boundary, and in both states before and after the change
At room temperature, only one specific state can exist. That is,
The other condition is the heat or heat required for that condition to manifest.
Is maintained while cold is applied, but the heat or
When the application of cold heat stops, it returns to the normal temperature range.
A so-called small hysteresis for temperature-color density due to temperature change
This is a type that changes color by indicating the lysis width (ΔH).

Also, Japanese Patent Publication No. 4-171 proposed by the present applicant.
No. 54, JP-A-7-179777, JP-A-7-179777
The thermosensitive color-changing color memory composition which exhibits large hysteresis characteristics and discolors described in, for example, JP-A-33997, that is, the shape of a curve in which the change in coloring density due to temperature change is plotted indicates the temperature in the color changing temperature range. This is a type in which the color changes following a significantly different path between the case where the temperature is raised from the lower temperature side and the case where the temperature is lowered from the higher temperature side than the color change temperature range. A reversible thermochromic composition having a characteristic of being able to memorize and retain a state changed at a temperature lower than the low-temperature side discoloration point or higher than the high-temperature side discoloration point in the normal temperature range is also effective.

The reversible thermochromic composition containing the above-described three components of an organic compound medium that reversibly causes a color reaction between the electron-donating color-forming organic compound and the electron-accepting compound is effective even when applied as it is. However, it is preferable to use it encapsulated in microcapsules. That is, under various use conditions, the reversible thermochromic composition is maintained at the same composition and can exert the same function and effect. By being encapsulated in the microcapsules, a chemically and physically stable pigment can be constituted, and the range of particle diameter of 0.1 to 100 μm, preferably 1 to 50 μm, more preferably 2 to 30 μm satisfies practicality. The microencapsulation is carried out by a conventionally known interfacial polymerization method, in situ polymerization method, in-liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melting dispersion cooling method, air suspension. There are a coating method, a spray drying method, and the like, which are appropriately selected according to the application. Further, a secondary resin film may be further provided on the surface of the microcapsule according to the purpose to impart durability, or the surface characteristics may be modified for practical use.

In the above-described constitution of the discolorable coloring book, a protective layer and a light stabilizer layer may be appropriately provided. Specifically, the light stabilizer layer is selected from an ultraviolet absorber, an antioxidant, an antioxidant, a singlet oxygen quencher, a superoxide anion quencher, an ozone decolorant, a visible light absorber, and an infrared absorber. This is a layer in which the light stabilizer is fixed in a dispersed state.
In addition, an anti-aging agent, an antistatic agent, a polarity-imparting agent, a thixotropic agent, an antifoaming agent and the like can be added to each layer as needed to improve the function.

In order to change the color of the coloring book, it is necessary to absorb water into the porous layer. As a method of attaching water to the discoloration coloring book, a method of wetting a finger with water to bring it into a water-absorbing state, a method of wetting an applicator or a sponge having a brush ear, a fiber pen body, or the like at the tip with water are used. And a method in which a container containing water is brought into close or contact with a discolorable coloring book, and water is drawn out from the container to make it a water-absorbing state. In addition, as a method of bringing a container containing water close to or in contact with the discolorable coloring book, drawing out the water from the container and bringing it into a water-absorbing state, storing the water in the container, and
A method of applying water by providing a fibrous body or a brush for drawing out water in a container, a method of containing water in a container, and a method of spraying water by providing a spray device, a method of spraying water in a container like a syringe To eject water. Further, a method in which water and a liquid-absorbing material such as sponge are accommodated in a container to have a shape imitating a stamp table, and the liquid may be pressed against the liquid-absorbing material to absorb water. In particular, an applicator having a brush ear, a fiber pen body, or the like at the tip, or a container for containing water, and a fiber body or a brush for drawing out the water in the container is provided to apply water. The applicator is suitable for the coloring book of the present invention, and a discolorable coloring book set can be configured in combination with the coloring book.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION As a specific embodiment of the discolorable coloring book of the present invention, for example, a non-discolorable image is provided on a sheet-like support, and a porous layer is provided on the image. Coloring book, a discolorable coloring book in which a porous layer is provided on a sheet-shaped support, and a non-discolorable contour image is provided on the porous layer, or
It is a discolorable coloring book in which a non-discolorable image and a porous image are juxtaposed on a sheet-like support, and the color tone of the lower layer is visually recognized by attaching water to the porous layer or the porous image to make a water absorbing state. This is a discolorable coloring book that makes the image look as if it were painted. When the porous layer or the porous image is dried, it returns to its original state. Examples of the means for adhering water include an applicator having a brush ear or a fiber pen body at the tip, a discoloring tool configured to contain water in the barrel and to be able to draw out water from the fiber pen body at the tip. Is preferable, and a discolorable coloring book set can be formed by combining the coloring book with the coloring book.

[0027]

Examples are shown below. The parts in the examples are parts by weight. Example 1 (See FIGS. 1 and 2) On a yellow synthetic paper as a support 3, 5 parts of a green pigment, 50 parts of an acrylate emulsion (50% solids), 0.2 part of a silicone-based defoamer, and a thickener 3 parts, wetting agent 2 parts,
1 part of leveling agent, 10 parts of water, epoxy crosslinking agent 2.5
Parts of the tulips were printed using a green printing ink that was mixed and stirred uniformly, and 5 parts of pink pigments were printed.
Acrylic ester emulsion (solid content 50%) 50
Part, silicone defoamer 0.2 part, thickener 3 parts, wetting agent 2 parts, leveling agent 1 part, water 10 parts, epoxy type cross-linking agent 2.5 parts, uniformly mixed and stirred pink printing Non-color-changing image 4 by printing a tulip flower image using ink
Was formed. Then, on the portion of the non-discoloring image 4 where the flower image is printed, finely divided silica (manufactured by Nipsil E-200) manufactured by a wet method as a low refractive index pigment.
A, manufactured by Nippon Silica Industry Co., Ltd.] 15 parts, an aqueous urethane resin as a binder resin [trade name: Hydran AP-1]
0, polyester-based urethane resin, solid content 30%, manufactured by Dainippon Ink and Chemicals, Inc.] 50 parts, water 30 parts, silicone-based antifoaming agent 0.5 parts, water-based ink thickener 3 parts, ethylene glycol 1 And 2 parts of an epoxy-based crosslinking agent were uniformly mixed and stirred, and printing was performed using a white printing ink to form a porous layer 5, thereby obtaining a discolorable coloring book 2.

The discoloring coloring set 1 is constituted by combining the dispensing coloring book 2 with the applicator 8 for storing water in the barrel, drawing out the water in the container and applying the water from the fiber pen body. did. When the pen body of the applicator 8 is applied in contact with the porous layer 5, the porous layer 5 absorbs water and becomes transparent,
Because the pink color due to the non-discoloring image 4 in the lower layer is visible,
You can see the white tulips painted pink.

The above appearance was observed at room temperature of 24 ° C. for about 3 minutes, but gradually became white as the porous layer dried, and returned to the original white tulip after about 10 minutes. The appearance change can be repeatedly performed, which is convenient.

Example 2 (not shown) On a white synthetic paper as a support, 5 parts of a black pigment, 50 parts of an acrylate emulsion (50% solid content), 0.2 parts of a silicone-based defoamer, a thickener 3 parts, 2 parts of a wetting agent, 1 part of a leveling agent, 10 parts of water, and 2.5 parts of an epoxy crosslinking agent were uniformly mixed and stirred, and a black printing ink and a red pigment 5 were stirred.
Parts, acrylate emulsion (solid content 50%)
50 parts, 0.2 parts of silicone defoamer, 3 parts of thickener, 2 parts of wetting agent, 1 part of leveling agent, 10 parts of water, 2.5 parts of epoxy cross-linking agent uniformly mixed and stirred red printing Ink, 5 parts of blue pigment, 50 parts of acrylate emulsion (50% solid content), 0.1 part of silicone defoamer.
2 parts, 3 parts of a thickener, 2 parts of a wetting agent, 1 part of a leveling agent, 10 parts of water, and 2.5 parts of an epoxy-based cross-linking agent were uniformly mixed and stirred, and a plurality of butterflies were prepared using a blue printing ink. The image was printed to form a non-discolorable image. Then, fine silica particles produced by a wet method as a low refractive index pigment [trade name:
Nip Seal E-200A, manufactured by Nippon Silica Industry Co., Ltd.]
15 parts, aqueous urethane resin (trade name: Hydran AP-10, polyester-based urethane resin, solid content 30%, manufactured by Dainippon Ink and Chemicals, Inc.) as a binder resin 5
0 parts, 30 parts of water, 0.5 parts of a silicone-based antifoaming agent, 3 parts of a water-based ink thickener, 1 part of ethylene glycol, and 2 parts of an epoxy-based crosslinking agent were uniformly mixed and stirred using a white printing ink. Solid printing was performed on the entire surface to form a porous layer to obtain a discolorable coloring book. In the color-change coloring book, a butterfly pattern with a slightly non-color-change image is visually observed in a dry state.

When the pen body of the applicator of Example 1 is applied to the discolorable coloring book in contact with the porous layer at the portion where the non-discolorable image is slightly visible, the porous layer absorbs water and becomes transparent. Since the images of the black, red, and blue butterflies due to the lower non-color-changing layer are seen, the state where the butterfly images are painted in black, red, and blue is seen.

The above appearance was visually observed at room temperature of 24 ° C. for about 3 minutes, but gradually became white as the porous layer dried, and returned to its original state after about 10 minutes. The appearance change can be repeatedly performed, which is convenient.

Example 3 (see FIG. 3) Fine silica particles produced by a wet method as a low refractive index pigment on brown synthetic paper as a support 3 [trade name: NIPSEAL E-74P, manufactured by Nippon Silica Industry Co., Ltd.] 15 parts, an aqueous urethane resin as a binder resin (trade name: Hydran AP-10, polyester-based urethane resin, solid content 30%, manufactured by Dainippon Ink and Chemicals, Inc.) 50 parts, water 3
0 parts, 0.5 parts of a silicone-based defoamer, 3 parts of a water-based ink thickener, 1 part of ethylene glycol, and 2 parts of an epoxy-based cross-linking agent were uniformly mixed and subjected to solid printing using a stirred white printing ink. To form a porous layer 5 and further 5 parts of a black pigment, an acrylate emulsion (solid content 5%)
0%) 50 parts, silicone antifoam 0.2 part, thickener 3
Parts, 2 parts of wetting agent, 1 part of leveling agent, 10 parts of water, 2.5 parts of epoxy cross-linking agent uniformly mixed, stirred and printed the outline of bear using black printing ink, non-discoloring contour image 6 was formed to obtain a discolorable coloring book 2.

A discolorable coloring book set was constructed by combining the dispensing coloring book 2 with the applicator for storing water in the barrel, drawing out the water in the container and applying the water from the fiber pen body, and Not shown). When the pen body of the applicator is applied while being brought into contact with the porous layer 3 in the non-discolorable contour image 4, the porous layer absorbs water and becomes transparent, and a brown image by the lower support is visually recognized. You can see the white bear on the brown bear.

The above appearance was observed at room temperature of 24 ° C. for about 3 minutes, but gradually became white as the porous layer dried, and returned to the original white bear after about 10 minutes. The above-mentioned appearance change can be repeatedly performed, and it can be easily applied along the contour image, so that it has convenience.

Example 4 (see FIG. 4) 5 parts of a blue pigment, 50 parts of an acrylate emulsion (50% solid content), 0.2 part of a silicone-based antifoaming agent, and thickening on a white synthetic paper as a support 3 3 parts, wetting agent 2 parts,
1 part of leveling agent, 10 parts of water, epoxy crosslinking agent 2.5
The image of the dolphin was printed using a blue printing ink in which the portions were uniformly mixed and stirred to form a non-discolorable image 4. Then
15 parts of fine silica particles manufactured by a wet method as a low refractive index pigment (trade name: Nipseal E-74P, manufactured by Nippon Silica Industry Co., Ltd.), aqueous urethane resin as a binder resin [trade name: Hydran AP-10, polyester] Urethane resin, solid content 30%, manufactured by Dainippon Ink and Chemicals, Inc.] 50 parts, water 30 parts, silicone-based defoamer 0.
5 parts, water-based ink thickener 3 parts, ethylene glycol 1
Parts, 2 parts of an epoxy cross-linking agent were uniformly mixed and stirred, and the whole surface was printed using a white printing ink to form a porous layer 5. Further, 5 parts of a black pigment, an acrylic ester emulsion (solid content) 50%) 50 parts, silicone antifoam 0.2 part, thickener 3 parts, wetting agent 2 parts, leveling agent 1
Parts, 10 parts of water, and 2.5 parts of an epoxy-based cross-linking agent are uniformly mixed and stirred to print a non-discolorable contour image 6 corresponding to the contour of the non-discolorable image 4 using a black printing ink. Coloring book 2 was obtained.

A discolorable coloring book set was constructed by combining the dispensing coloring book 2 with the applicator for storing water in the barrel, drawing out the water in the container and applying the water from the brush, and the discolorable coloring book 2 (FIG. Not shown). When the brush of the applicator is applied while being brought into contact with the porous layer 3 in the non-discolorable contour image 4, the porous layer absorbs water and becomes transparent, so that the blue color of the lower non-discolorable image is visible. It can be seen that white dolphins are painted blue.

The above appearance was observed at room temperature of 24 ° C. for about 3 minutes, but gradually became white as the porous layer dried, and returned to the original white bear after about 10 minutes. The above-mentioned appearance change can be repeatedly performed, and it can be easily applied along the contour image, so that it has convenience.

Example 5 (See FIG. 5) Fine silica particles produced by a wet method as a low refractive index pigment on a polyester sheet colored pink as a support 3 [trade name: Nipseal E-74P, Japan Silica Industry Co., Ltd.] 15 parts, aqueous urethane resin as binder resin [trade name: Hydran AP-10, polyester-based urethane resin, solid content 30%, manufactured by Dainippon Ink & Chemicals, Inc.] 50 parts, water 30 Parts, a silicone-based antifoaming agent 0.5 parts, a water-based ink thickener 3 parts, ethylene glycol 1 part, and an epoxy-based cross-linking agent 2 parts are uniformly mixed and stirred to form a plurality of star-shaped inks. Is formed, and further, in a portion where the porous image 7 is not provided,
5 parts of black pigment, 50 parts of acrylic ester emulsion (50% solid content), 0.2 parts of silicone defoamer, 3 parts of thickener, 2 parts of wetting agent, 1 part of leveling agent, 10 parts of water, epoxy Using a black printing ink obtained by uniformly mixing and stirring 2.5 parts of a crosslinking agent, a non-discolorable image 4 was formed to obtain a discolorable coloring book 2.

A discolorable coloring book set was constructed by combining an applicator provided with a brush ear at the tip of the barrel and the discolorable coloring book 2 (not shown). When the brush of the applicator is impregnated with water and applied by contacting the porous layer 3, the porous layer absorbs water and becomes transparent, and a pink image is visually recognized by the lower support. You can see the star painted pink.

The above aspect was visually observed at room temperature of 24 ° C. for about 3 minutes, but gradually became white as the porous layer dried, and returned to the original white bear after about 10 minutes. The appearance change can be repeatedly performed, which is convenient.

[0042]

According to the present invention, there is provided a discolorable coloring book which is excellent in repetitive practicability, free of contamination since water is used as a coating tool used for coloring, and which is excellent in convenience and resource saving. A discolorable coloring book set can be provided.

[Brief description of the drawings]

FIG. 1 is a perspective view of one embodiment of a discolorable coloring book set of the present invention.

FIG. 2 is a vertical sectional view taken along the line AA of the coloring book of FIG. 1;

FIG. 3 is a longitudinal sectional view of another embodiment of the discolorable coloring book of the present invention.

FIG. 4 is a longitudinal sectional view of another embodiment of the color-change coloring book of the present invention.

FIG. 5 is a longitudinal sectional view of another embodiment of the discolorable coloring book of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Discolorable coloring book set 2 Discolorable coloring book 3 Support 4 Non-discolorable image 5 Porous layer 6 Non-discolorable contour image 7 Porous image 8 Discoloration tool

Claims (5)

[Claims] 1. A porous material comprising: a non-color-change image provided on a support; and a porous layer in which a low refractive index pigment is fixed in a dispersed state together with a binder resin on at least a part of the non-color change image. A discolorable coloring book in which a layer becomes transparent or translucent in a water-absorbing state and a non-discolorable image can be viewed. 2. A porous layer in which a low-refractive-index pigment is fixed in a dispersed state together with a binder resin on a support, and a non-discoloring contour image is provided on the porous layer, wherein the porous layer is in a water-absorbing state. A discolorable coloring book that allows you to see the color of the lower layer by making it transparent or translucent. 3. The discolorable coloring book according to claim 2, wherein a non-discolorable image corresponding to the contour of the non-discolorable contour image is provided between the support and the porous layer. 4. A non-color-change image and a porous image in which a low-refractive index pigment is fixed in a dispersed state together with a binder resin on a support, and the lower layer is made transparent or translucent in a water-absorbing state. Discoloration coloring book where you can see the color tone of the color. 5. A discoloring tool for applying water, and a discoloring tool for applying water.
A discolorable coloring book set comprising the discolorable coloring book of any of the above.