JP2000135386A - Target whose color is changed by water - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reversibly express the different looks from its normal condition by a water-sticking means by providing a porous layer that consists of a micro- grain silica made by wet method and a binder resin on a supporting body and composing it so that it can reversibly change its looks into different one from that of its normal condition when water is soaked into the porous layer. SOLUTION: For a supporting body 2, a white ink for screen printing, e.g. the one made by homogeneously mixing and agitating 15 pts. wet method-made micro-grain silica, 30 pts. urethane emulsion, 50 pts. water, 0.5 pt. silicone defoaming agent, 3 pts. thickener for water ink, 1 pt. ethylene glycol and 3 pts. block isocyanate cross-linking agent, is solidly set on a pink nylon taffeta, dried and hardened so as to shape a porous layer 3. In a target 1 of which the color is changed by water, when it is in a dried condition, white color of the porous layer 3 is seen and pink color of the supporting body 2 is not seen. When water is stuck to the target 1 by a water pistol, the porous layer 3 becomes transparent and pink color of the supporting body 2 becomes visible.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a water discolorable target. More specifically, the present invention relates to a water-discolorable target that shows different aspects in a dry state and a state impregnated with water through a water-adhering means.

[0002]

2. Description of the Related Art Conventionally, a film provided with a porous layer containing a low-refractive index pigment and a backing on which an image has been formed are adhered to each other. A water image sheet for displaying an image provided in the game is disclosed, and it is also disclosed that the water image sheet is used as a target of a survival game (Japanese Patent Publication No. 5-15).
389). In the above-described water image sheet, the lower layer is hidden by the porous layer in a dry state (non-liquid absorbing state),
Although the image provided in the lower layer becomes transparent when liquid such as water is absorbed in the porous layer, the transparency in the liquid absorbing state is impaired when the concealing property of the porous layer is improved, and conversely,
If the amount of the low-refractive-index pigment added is reduced in order to improve the transparency in the liquid-absorbing state, a drawback such as impairing the hiding power in a dry state occurs. In particular, when the color tone of the lower layer is a color tone having a relatively high lightness value such as a fluorescent color, it is necessary to increase the content of the low refractive index pigment in order to conceal this color tone, thereby increasing the liquid absorption state. Transparency is impaired, making it difficult to see clear colors. Therefore, the target provided with the porous layer can visually confirm the appearance after the change before attaching water to the target, or the appearance change before and after the change even when the water is attached is poor, and lacks interest. Was something.

[0003]

SUMMARY OF THE INVENTION The present invention is to solve the problem of the conventional target provided with a porous layer, that is, to improve both the concealing property in a dry state and the transparency in a liquid absorbing state. Satisfactory, it is possible to effectively function the target play that reversibly reveals an aspect different from the normal state through water attachment means such as spraying water with a water gun or throwing an impregnated body impregnated with water. It is intended to provide a water discoloration target.

[0004]

SUMMARY OF THE INVENTION The present invention provides a method for manufacturing a semiconductor device comprising the steps of:
A porous layer containing at least particulate silica and a binder resin produced by a wet method is provided, and the porous layer is impregnated with water through a means for adhering water, and reversibly changes to an aspect different from a normal state. Require a water-discolorable target configured as possible. Furthermore, the binder resin is a urethane-based resin, the support is a fabric, the water-discolorable target is in the form of clothing or a hat, water attaching means,
The requirement is that the water be sprayed by a water gun or the impregnated body impregnated with water be thrown.

The porous layer containing the low refractive index pigment has a hiding property in a normal state, that is, in a dry state, has a white color, and is transparent or semi-transparent in a state in which a liquid such as water is absorbed by applying a water gun or the like. Transparent to reveal lower layer color tone. 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, and a refractive index of 1.4 to Although those having a range of 1.7 are generally used, the present invention has been intensively studied in order to satisfy both the concealing property in a normal state and the transparency in a liquid absorbing state. It has been found that the above problem can be solved by using, as the low-refractive-index pigment, fine-particle silicic acid produced by a wet method among fine-particle silicic acids (hereinafter, referred to as wet-process fine-particle silicic acid).

The finely divided silica 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 a silicon halide such as silicon tetrachloride (hereinafter referred to as a dry method). Method referred to as fine particulate silica)
Although it is roughly classified into a wet method using a liquid phase reaction such as decomposition with an acid such as sodium silicate, as described above, as a particulate silica used for satisfying the concealing property of the porous layer in a normal state, The most suitable is fine particles of wet-process silica. This is because the dry process particulate silica and the wet process particulate silica have different structures, and the dry process particulate silica forms a three-dimensional structure in which silicic acid is tightly coupled as shown below,

Embedded image The wet-processed particulate silica has a so-called two-dimensional structure in which the silica is condensed to form a long molecular arrangement as shown below. 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.

Embedded image Further, the low-refractive-index pigment contained in the porous layer is mainly a water-absorbing medium, so that the wet-process fine-particle silicic acid is present as a silanol group on the particle surface compared to the dry-process fine-particle silicic acid. It is preferably used because it has a large number of hydroxyl groups and therefore has an appropriate degree of hydrophilicity. In order to adjust the concealing property of the porous layer in the normal state and the transparency in the liquid absorbing state, the above-mentioned low refractive index pigment may be used in combination with the wet method particulate silica.

[0007] The wet-processed particulate silica in the porous layer is
Although it depends on properties such as particle diameter, specific surface area, and oil absorption, in order to satisfy both the hiding property in the normal state and the transparency in the liquid absorbing state, the coating amount is 1 g / m ^{2 to} 30 g / m ^2. And more preferably 5 g / m ^{2 to} 20 g / m ^2.
It is. If it is less than 1 g / m ² , it is difficult to obtain sufficient concealing properties under normal conditions, and if it exceeds 30 g / m ² , it is difficult to obtain sufficient transparency when absorbing liquid. The particle size of the particulate silica is not particularly limited, but may be 0.0
Those having a size of 3 to 10.0 μm are preferably used.

The particulate silica is dispersed in a vehicle containing a binder resin as a binder, applied to a support, and 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 each of the above resin emulsions, casein,
Examples include starch, cellulose derivative, polyvinyl alcohol, urea resin, phenol resin and the like. The mixing ratio of the particulate silica and these binder resins depends on the type and properties of the particulate silica, but preferably the binder resin solid content is 0.5 to 1 part by weight of the particulate silica.
It is 2 parts by weight, more preferably 0.8 to 1.5 parts by weight. When the binder resin solid content is less than 0.5 part by weight with respect to 1 part by weight of the particulate silica, it is difficult to obtain a practical film strength of the porous layer. In this case, the permeability of water into the inside of the porous layer becomes poor. 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 sufficient film strength. Therefore,
In the target of the present invention that requires abrasion resistance, it is preferable to use a nylon resin or a urethane-based resin as the above-mentioned binder resin, or to contain at least the resin. As the urethane-based resin, polyester-based urethane resin, polycarbonate-based urethane resin,
There are polyether-based urethane resins and the like, and two or more kinds can be used in combination. Also, the above resin is self-emulsified by the ionic groups of a urethane emulsion resin in which water is emulsified and dispersed in water, or an ionic urethane resin (urethane ionomer) itself without requiring an emulsifier, and a colloid dissolved and dispersed in water. 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, but in the present invention, an aqueous urethane-based resin, particularly, a urethane-based emulsion resin or a colloid-dispersed urethane-based resin is preferable. Used for The urethane-based resin can be used alone, but other binder resins can be used in combination depending on the type of the support and the performance required for the film. When a binder resin other than the urethane resin is used in combination, in order to obtain a practical film strength, it is preferable that the binder resin of the porous layer contains the urethane resin in a solid content weight 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. The binder resin has different degrees of affinity with water, but by combining these, the penetration time into the porous layer, the degree of penetration into the porous layer, and the drying speed after penetration can be adjusted. Further, the adjustment can be controlled by adding a dispersant as appropriate.

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 diversified by adding a metallic luster pigment such as bismuth chloride or adding a general dye or pigment, a fluorescent dye or a fluorescent pigment. Furthermore, if hot water or cold water is applied, the porous layer contains a reversible thermochromic composition that reversibly changes color due to temperature change, or a reversible thermochromic layer containing the reversible thermochromic composition is provided. By doing so, the color change can be further diversified.

The reversible thermochromic composition is, for example, a reversible thermochromic composition containing three components of an electron-donating color-forming organic compound, an electron-accepting compound, and an organic compound medium for reversibly causing a color reaction between the two. Discoloring composition (JP-B-51-3541)
No. 4, JP-B-51-44706, JP-B-51-44706
-44708, JP-B-52-7774, JP-B-1-29398, JP-A-7-186540, JP-B-1-17154, and JP-A-7-179.
777, JP-A-7-33997), liquid crystal, Ag ₂ HgI ₄ , Cu ₂ HgI _{4 and the} like.

The above-described reversible thermochromic composition containing three components of an organic compound medium which 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 preferably used as a microcapsule pigment 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,
Particle size 0.1-100 μm, preferably 1-50 μm,
More preferably, the range of 2 to 30 μm satisfies the 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 coating method, spray drying method, etc.
It is 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.

The reversible thermochromic composition (preferably, microcapsule pigment) is dispersed in a vehicle containing a resin which is a film-forming material, applied as a coloring material such as ink or paint, and reversibly thermochromic. Layers can be formed. or,
It may be dispersed in a thermoplastic resin or a thermosetting resin, molded into a sheet or other various forms, and applied as a layer having a reversible thermochromic layer. Incidentally, non-thermochromic general dyes and pigments, fluorescent dyes and fluorescent pigments and the like can be mixed in the reversible thermochromic layer to cause various color changes.

As the support for forming the target, in addition to fabrics such as woven fabrics, knitted fabrics, braids, and nonwoven fabrics, paper, synthetic paper, synthetic leather, leather, plastic, glass, ceramics, wood, stone, and the like can be used. And all are valid. Preferably as the support, water-resistant fabric, synthetic leather,
In the case of using a fabric as a support, it is preferably a woven fabric whose surface is excellent in smoothness from the viewpoint of the film forming property of the porous layer. When a cloth is used as the support, compared to a non-porous support such as a plastic film, even if supersaturated water adheres, the cloth can absorb or drip and reduce or prevent water dripping, and the location where water is attached is clear. A target that can be visually recognized can be obtained. The cloth provided with the porous layer may be used as a target itself, or may be cut into an appropriate shape, then sewn to produce clothing or a hat, and attached to various articles. , Can also be sewn. In addition, when the smoothness of the fabric surface is poor, or when the permeability of the ink or the like into the fabric is large and the film forming property of the porous layer is poor, the fabric should be subjected to a treatment such as water repellency. Thereby, the film forming property of the porous layer can be improved.

As the method for forming the porous layer, conventionally known coating methods, for example, printing means such as screen printing, offset printing, gravure printing, coater, tampo printing, transfer, brush coating, spray coating, static coating, etc. Electric painting,
Examples include electrodeposition coating, flow coating, roller coating, dip coating, and the like.

Further, the water-discolorable target of the present invention may be provided with a non-discolorable layer by applying a non-discolorable ink containing a general dye or pigment, a fluorescent dye or a pigment, or a titanium dioxide-coated mica, iron oxide or the like, if necessary. -A metallic gloss layer can be provided by applying an ink containing a metallic gloss pigment such as titanium dioxide-coated mica, iron oxide-coated mica, guanine, sericite, basic lead carbonate, lead acid arsenate, bismuth oxychloride and the like. In particular, in the present invention, even when a non-discoloring layer containing a fluorescent dye or a fluorescent pigment is provided below the porous layer, it is possible to conceal a fluorescent color having a relatively high lightness value, and to perform color change between a normal state and a liquid absorbing state. A target with a high degree of freedom is obtained. In addition, 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 quencher, a visible light absorber, and an infrared absorber. This is a layer in which the light stabilizer is fixed in a dispersed state. Incidentally, an antistatic agent, a polarity imparting agent,
If necessary, a thixotropic agent, an antifoaming agent, etc. may be added to each layer to improve the function.

Next, the structure of the water-discolorable target of the present invention and the change in a dry state (non-liquid absorbing state) and a state in which water or the like is absorbed will be described. As described above, the water-discolorable target of the present invention has a porous layer containing a low-refractive-index pigment and a binder resin laminated on a support, and has a concealing property when dried to conceal the lower layer, It becomes transparent or translucent while absorbing water or the like to make the lower layer visible. Therefore, even if the support is of a single color, by partially wetting the porous layer by means of water attachment, the wetted part becomes transparent or translucent and the color tone of the lower layer is visually recognized, and a desired image is displayed. Can be put out.
When the water in the porous layer evaporates and dries, the porous layer again conceals the lower layer and returns to the original state. Since the porous layer is a layer containing wet-processed particulate silica, the opacity during drying is high, and the color tone of the lower layer can be completely concealed. It is possible to obtain a target with a very bright tone. Therefore, not only can a pattern or a multicolor pattern be provided on a support and concealed by a porous layer, but also a pattern that is related or integrated with a pattern that is visible in a state where the porous layer is made transparent by liquid absorption can be used. It is also possible to provide an image on the layer and visually recognize an image in which the symbols are combined in a liquid absorbing state. In addition, it is also possible to form a pattern with a porous layer colored by adding a general pigment or the like, so that the porous layer absorbs liquid and becomes visually indistinguishable by the color of the support which is seen through. In addition, the color tone of the porous layer can be set. Further, as a transparent support, for example, a porous layer may be provided on a transparent three-dimensional object, and the porous layer may be made transparent by absorbing liquid to see through the three-dimensional object itself.

In the above-described structure, the porous layer may be a pattern layer such as a character, a symbol, a figure, etc., if necessary. or,
A reversible thermochromic layer or a non-color-changing layer may be interposed or provided on an upper layer, and similarly, it may be a design layer of characters, symbols, figures, and the like.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The water-discolorable target of the present invention is not limited to a planar shape, but various shapes such as a linear shape, an uneven shape, and a three-dimensional shape are effective. As a specific embodiment of the water discoloration target,
For example, a porous layer is provided on stuffed animals, dolls, costumes for dolls, riding toys, dresses, swimwear, raincoats, clothing and hats, helmets, socks, shoes, recreational tools used in various water games, artificial flowers, etc. Can form a target. As a means for spraying water on the target, a water gun for spraying water is preferably used, but water is sprayed by a hose or shower connected to a tap, or a hose or shower connected to a device for pressurizing water. Spraying water, spraying atomized water with a spraying device such as a sprayer, throwing impregnated objects such as sponges impregnated with water, soft gel materials containing water, or ice chips or snowballs Alternatively, it may be a method of throwing a capsule that is destroyed by an impact containing water, loading the capsule into a model gun and firing it, or spraying water by hand.

[0019]

Examples are shown below. The parts in the examples are parts by weight. Example 1 (see FIG. 1) Wet method fine powder silica [trade name: Nip Seal E-2] on the entire surface of pink nylon taffeta cloth as support 2
00, manufactured by Nippon Silica Industry Co., Ltd.), 15 parts, urethane emulsion [trade name: Hydran HW-930, manufactured by Dainippon Ink and Chemicals, Inc., solid content: 50%], 30 parts, water 50
Parts, a silicone-based antifoaming agent 0.5 parts, a water-based ink thickener 3 parts, ethylene glycol 1 part, and a blocked isocyanate-based crosslinking agent 3 parts are uniformly mixed and stirred using a white screen printing ink. Solid printing was performed on an 80-mesh screen plate, and dried and cured at 130 ° C. for 5 minutes to form a porous layer 3 to obtain a water-discolorable target 1.

In the water-discolorable target 1, the white color due to the porous layer 3 is visible in a dry state, and the pink color of the support 2 is not visible. When water is attached to the water-discolorable target 1 using a water gun, the porous layer 3 in the attached portion becomes transparent, and a vivid pink color due to the lower support 2 is seen. Further, since the cloth absorbs water, dripping of water adhering to the target was suppressed, and the practicality as the target was excellent. The appearance was pink when water adhered, but turned white when dried and water evaporated from the fabric, and this phenomenon could be repeated many times.

Example 2 (see FIG. 2) Green pigment [trade name: Sundai Super Green LX]
B, Sanyo Dyeing Co., Ltd.] 5 parts, acrylic ester emulsion [trade name: Movinyl 763, Hoechst Gosei Co., Ltd., solid content 48%] 50 parts, aqueous ink thickener 3 parts, leveling agent Using a green screen printing ink prepared by uniformly mixing and stirring 0.5 part, an antifoaming agent 0.3 part, and an epoxy-based cross-linking agent 5 parts, using a 180-mesh screen plate, solid printing was performed at 100 ° C. After drying and curing for 3 minutes, a non-discoloring layer 4 was formed. Then, on the entire surface of the non-discoloring layer 4, wet-process fine powder silica [trade name: Nip Seal E-2]
20, manufactured by Nippon Silica Kogyo Co., Ltd.], 15 parts, yellow pigment [trade name: Sundai Super Yellow 10GS, manufactured by Sanyo Dye Co., Ltd.], 1 part, urethane emulsion [trade name: Hydran AP-20, Dainippon Ink & Chemicals, Ltd.] 45 parts, water 40 parts, silicone defoamer 0.5 part, thickener for aqueous ink 3 parts, ethylene glycol 1 part, blocked isocyanate cross-linking agent 3 parts Using a yellow screen printing ink formed by mixing and stirring uniformly, solid printing was performed on a 100 mesh screen plate,
After drying and curing at 130 ° C. for 5 minutes, the porous layer 3 was formed to obtain a water-discolorable fabric. After cutting the water discolorable fabric,
The children's jacket was sewn to obtain the water discolorable target 1.

The water-discolorable target 1 is practically used for a survival game using a water gun. In a dry state, the yellow color due to the porous layer 3 is visible and the green color due to the non-discolorable layer 4 is not visible. When water is attached to the water-discolorable target 1 using a water gun, the porous layer 3 in the attached portion becomes transparent, and a bright green color due to the lower non-discolorable layer 4 is seen. Further, since the cloth absorbs water, dripping of water adhering to the target was suppressed, and the practicality as the target was excellent. The above aspect is green when water is attached, but turns yellow when water evaporates from the fabric after drying, and this phenomenon can be repeated many times, thereby enhancing the playability of the survival game. Was completed.

Example 3 (see FIG. 3) 7 parts of a red pigment (trade name: TC Red FG (S), manufactured by Dainichi Seika Co., Ltd.) on a white cotton T-shirt cloth as a support 2; Acrylic ester emulsion [Product name:
Movinyl 763, Hoechst Gosei Co., Ltd., solid content 4
8%] using a red screen printing ink prepared by uniformly mixing and stirring 50 parts of an aqueous ink thickener, 3 parts of a leveling agent, 0.5 parts of a leveling agent, 0.3 parts of an antifoaming agent and 5 parts of an epoxy crosslinking agent. Then, a circular shape was printed using a 180-mesh screen plate, and dried and cured at 100 ° C. for 3 minutes to form a non-discoloring layer 4. Then, on the non-discoloring layer 4, 15 parts of wet-process fine powder silica (trade name: Nip Seal E-1009, manufactured by Nippon Silica Industry Co., Ltd.) and urethane emulsion [trade name: Hydran AP-10, Dainippon Ink and Chemicals, Ltd.] 45 parts, water 40 parts, silicone defoamer 0.5 part, thickener for aqueous ink 3 parts, ethylene glycol 1 part, blocked isocyanate cross-linking agent 3 parts Using a white screen printing ink formed by uniformly mixing and stirring, a circle slightly larger than the circle of the non-discoloring layer 4 is printed on an 80 mesh screen plate,
Drying and curing at 5 ° C. for 5 minutes to form the porous layer 3 to obtain a water-discolorable fabric. After cutting the water discolorable cloth, a T-shirt was sewn to obtain a water discolorable target 1.

In the water-discolorable target 1, when the porous layer 3 is white in a dry state, a white T-shirt is visible on the entire surface, and the red color due to the non-discolorable layer 4 is not visible. When water is attached to the water discolorable target 1 at a portion where the porous layer 3 is provided by using a water gun, the porous layer 3 becomes transparent and a bright red circle by the lower non-discolorable layer 4 is visually recognized. You. Further, since the cloth absorbs water, dripping of water adhering to the target was suppressed, and the practicality as the target was excellent. The appearance was red when water was attached, but turned white when the water dried and the water evaporated from the fabric, and this phenomenon could be repeated many times. In addition, when a survival game using a water gun was performed while wearing the water-discolorable target 1, even if water adhered to a position different from the portion where the porous layer 3 was provided, the water-discolorable target 1 was not discolored. When water adheres to the portion where the layer 3 is provided, the color changes to red, so that the appearance of blood bleeding is visually recognized, and the water-discolorable target 1 having high playability was obtained.

Example 4 (see FIG. 4) 7 parts of a red pigment (trade name: TC Red FG (S), manufactured by Dainichi Seika Co., Ltd.) on the whole surface of a white polyester satin cloth as a support 2, acrylic 50 parts of acid ester emulsion [trade name: Movinyl 763, manufactured by Hoechst Gosei KK, solid content 48%], 3 parts of aqueous ink thickener, 0.5 parts of leveling agent, 0.3 parts of defoamer, epoxy Using a red screen printing ink prepared by uniformly mixing and stirring 5 parts of a system cross-linking agent, solid printing was performed on a 180-mesh screen plate, and dried and cured at 100 ° C. for 3 minutes to form a non-discoloring layer 4.
Was formed. Next, on the entire surface on the non-color-changing layer 4, wet-process finely-divided silica [trade name: Nip Seal E-1009,
Nippon Silica Industry Co., Ltd.] 15 parts, urethane emulsion [trade name: Hydran AP-20, manufactured by Dainippon Ink and Chemicals, Inc., solid content 30%] 25 parts, water-soluble Nanron resin solution [trade name: 20 parts of Toresin FS-350, manufactured by Teikoku Chemical Industry Co., Ltd., solid content 35%], 1 part of yellow pigment [Sandai Super Yellow 10GS, manufactured by Sanyo Pigment Co., Ltd.], 40 parts of water, silicone based Foaming agent 0.
5 parts, thickener for water-based ink 3 parts, ethylene glycol 1
Parts, 3 parts of a blocked isocyanate-based cross-linking agent, and 8 parts of yellow ink for screen printing.
Solid printing was performed on a 0-mesh screen plate, followed by drying and curing at 130 ° C. for 5 minutes to form a porous layer 3 to obtain a water-discolorable fabric. The water-discolorable fabric was cut into a circular shape having a diameter of 10 cm, and was sewn as clothing 6 on the chest of a yellow jacket to obtain a water-discolorable target 1.

In the water-discolorable target 1, when the porous layer 3 exhibits a yellow color in a dry state, the entire surface of the water-discolorable target 1 has a yellow jacket, and the red color of the non-discolorable layer 4 is not visible. When water is adhered to the water discolorable target 1 using a water gun on a portion where the porous layer 3 is provided on the chest using a water gun, the porous layer 3 becomes transparent and a bright red circle formed by the lower non-discolorable layer 4 is formed. Visualized. Further, since the cloth absorbs water, dripping of water adhering to the target was suppressed, and the practicality as the target was excellent. The appearance was red when water was attached, but it turned yellow when water was evaporated from the fabric after drying, and this phenomenon could be repeated many times. In addition, when a survival game using a water gun was performed while wearing the water-discolorable target 1, even if water adhered to a position different from the portion where the porous layer 3 was provided, the discoloration did not occur.
When water adheres to the portion where the porous layer 3 is provided, the color changes to red, so that the appearance of blood bleeding is visually recognized, and the water-discolorable target 1 having high playability was obtained.

Example 5 (see FIG. 5) A white PET film (100 μm thick) was used as the support 2.
m) On top, using a red aqueous screen printing ink,
The flame pattern was printed on a 180-mesh screen plate to form the non-discoloring layer 4. Then, on the entire surface of the non-discoloring layer 4, wet-process finely-divided silica [trade name: Nip Seal E-
1011, manufactured by Nippon Silica Kogyo Co., Ltd.] 15 parts, urethane emulsion [Neorez R-966, manufactured by Zeneca Co., Ltd., solid content 33%] 45 parts, water 40 parts, silicone antifoaming agent 0.1 part. 5 parts, thickener for water-based ink 3 parts,
Using a white screen printing ink prepared by uniformly mixing and stirring 1 part of ethylene glycol and 3 parts of a blocked isocyanate-based cross-linking agent, solid printing was performed on a 150-mesh screen plate, and dried and cured at 130 ° C. for 5 minutes to form a porous film. The quality layer A31 was formed. On the entire surface of the porous layer A31, wet-process fine silica powder (trade name: Nip Seal E-100)
9, Nippon Silica Industry Co., Ltd.] 15 parts, urethane emulsion [trade name: Hydran AP-20, Dainippon Ink Co., Ltd., solid content 30%] 25 parts, water-soluble nanlon resin solution [trade name: Toresin FS-350, manufactured by Teikoku Chemical Industry Co., Ltd. (solid content: 35%)], 20 parts of yellow water-dispersed pigment [trade name: Sundai Super Yellow 10GS, manufactured by Sanyo Pigment Co., Ltd.], 40 parts of water, Using a yellow screen printing ink prepared by uniformly mixing and stirring 0.5 part of a silicone-based antifoaming agent, 3 parts of a thickening agent for water-based ink, 1 part of ethylene glycol, and 3 parts of a blocked isocyanate-based cross-linking agent, 150 mesh Solid printing on the screen version of
After drying and curing at 30 ° C. for 5 minutes, a porous layer B32 was formed to obtain a water discolorable film. The water discolorable film,
It was cut into an oval shape so that the pattern of the non-discoloring layer 4 was inserted, and was adhered to the front surface of the white hat 7 using a hot melt adhesive to obtain a water discolorable target 1.

In the water-discolorable target 1, when the porous layer 32 exhibits a yellow color in a dry state, a yellow ellipse is visually recognized on the front surface of the cap, and the porous layer 31 exhibits a white color for further hiding. Since it is applied, the design of the flame by the non-discoloring layer 4 is not visually recognized. When water is attached to the water discolorable target 1 at a portion where the porous layer 32 is provided using a water gun, the porous layer 32 and the porous layer 31 become transparent, and the lower non-discolorable layer 4
A bright flame pattern is seen. In the above aspect, a flame pattern was visually observed in a state where water was attached, but the color became yellow when the water evaporated and dried, and this phenomenon could be repeated many times. Further, when the water discolorable target 1 is covered with water gun play, when water adheres to the portion where the porous layer 3 is provided, a flame pattern appears, so that the water discolorable target 1 having high playability is provided. Could be obtained.

Example 6 As a support, a fluorescent pink pigment [trade name: Epocolor FP-1000N,
Nippon Shokubai Co., Ltd.] 15 parts, acrylic ester emulsion [trade name: Movinyl 763, Hoechst Gosei Co., Ltd., solid content 48%] 50 parts, water-based ink thickener 3
Parts, 0.5 parts of a leveling agent, 0.3 parts of an antifoaming agent, and 5 parts of an epoxy-based cross-linking agent, using a fluorescent pink ink obtained by uniformly mixing and stirring, and performing a solid printing on a 120-mesh screen plate. After drying and curing at 100 ° C. for 3 minutes, a non-discoloring layer was formed. Then, on the non-discoloring layer 4, 15 parts of wet-processed finely divided silica (trade name: Nip Seal E-1011, manufactured by Nippon Silica Industry Co., Ltd.) and urethane emulsion [trade name: Hydran HW-920, Dainippon Ink and Chemicals, Ltd.] 45% of yellow pigment [trade name: manufactured by Kogyo Co., Ltd., solid content 50%]
Sundai Super Yellow 10GS, Sanyo Dyeing Co., Ltd.
1 part, 40 parts of water, 0.5 part of a silicone-based antifoaming agent, 3 parts of a thickener for water-based ink, 1 part of ethylene glycol, and 3 parts of a blocked isocyanate-based crosslinking agent are uniformly mixed and stirred. Printing ink and 15 parts of wet-process fine silica (trade name: Nip Seal E-1011, manufactured by Nippon Silica Industry Co., Ltd.), urethane emulsion [trade name: Hydran HW-920, Dainippon Ink and Chemicals, Inc.] , Solid content 50%] 45 parts, blue pigment [trade name:
Sundai Super Blue GLL, Sanyo Dyeing Co., Ltd.]
0.5 part, 40 parts of water, 0.5 part of silicone defoamer, 3 parts of thickener for water-based ink, 1 part of ethylene glycol, 3 parts of blocked isocyanate cross-linking agent Using each printing ink, 1
Print a polka dot pattern on a 09 mesh screen
After drying and curing at 30 ° C. for 5 minutes to form a porous layer, a water-discolorable fabric was obtained. After cutting the water discolorable cloth, a swimsuit for children was sewn to obtain a water discolorable target.

In the dry state where water is not attached, the water discolorable target is visually observed as a state in which a yellow and blue polka dot pattern is printed on a pink background by a non-discolor layer and a porous layer. Exhibits a vivid yellow and blue color without being affected by the underlying pink color. When water is attached to the water-discolorable target, the yellow opaque porous layer changes to an orange polka dot pattern that has become yellow transparent and mixed with the underlying pink color, and the blue opaque porous layer is blue transparent. It changed to a purple polka dot pattern that was mixed with the pink color of the lower layer.
The appearance was in the state in which water was attached, but when dried and the water evaporated from the fabric, the appearance became a yellow and blue polka dot pattern, which could be repeated many times.
In addition, when worn on a poolside or the like and played with water, the color changes due to the adhesion of water, so that a colorful and highly playable water-discolorable target can be obtained.

Example 7 (see FIG. 6) As a support 2, a character of "100 points" is placed at the center on a disk formed of HIPS, and "50" is placed at a position slightly away from the center.
The letters "dot" were printed using a blue oil-based screen printing ink to obtain a non-discoloring layer 4. Then, on the entire surface of the support 2 provided with the non-color-changing layer 4, wet-process finely-divided silica [trade name: Nip Seal E-1011, Nippon Silica Industry Co., Ltd.]
15 parts, urethane emulsion [brand name: Neor]
ez R-966, manufactured by Zeneca Corporation, solid content 33%] 4
5 parts, 40 parts of water, 0.5 parts of silicone defoamer, 3 parts of thickener for water-based ink, 1 part of ethylene glycol, 3 parts of blocked isocyanate-based cross-linking agent for white screen printing Using ink, solid printing was performed on a 150-mesh screen plate, followed by drying and curing at 130 ° C. for 5 minutes to form a porous layer A31. Further, on the porous layer A31, wet-process finely powdered silica (trade name: Nip Seal E-1009, manufactured by Nippon Silica Industry Co., Ltd.) 15
Part, urethane emulsion [trade name: Hydran AP-
20, Dainippon Ink and Chemicals, Inc., solid content 30%]
25 parts, water-soluble nylon resin solution [trade name: Toresin F
S-350, manufactured by Teikoku Chemical Industry Co., Ltd., solid content 35%] 2
0 parts, yellow pigment [Product name: Sundai Super Yellow 1]
0GS, Sanyo Dyeing Co., Ltd.] 1 part, water 40 parts, silicone defoamer 0.5 part, aqueous ink thickener 3 parts, ethylene glycol 1 part, blocked isocyanate crosslinking agent 3
Using a yellow screen printing ink formed by uniformly mixing and stirring the parts, a circle having a size covering the non-discoloring layer 4 is printed on a 150-mesh screen plate at 130 ° C.
After drying and curing for minutes, the porous layer B32 was formed to obtain the water-discolorable target 1.

In the water-discolorable target 1, in a dry state, a state in which a yellow circle of the porous layer 32 is drawn on a white background of the porous layer 31 is visually recognized, and the porous layer 31 exhibits a white color and is concealed. The character by the non-color-changing layer 4 is not visually recognized because the character is further provided. When a spherical sponge impregnated with water is thrown into the center of the water-discolorable target 1, the porous layer 31 is made transparent by water adhering to the portion hit by the sponge, and the porous layer 32 becomes yellow-transparent. The character of “100 points” mixed with the blue color by the non-color-change layer 4 appears, and the character of “50 points” appears when thrown at a position slightly away from the center of the water-discolorable target 1. I do. In the above aspect, the letters are visible when water is attached, but when the water evaporates and dries, a yellow circle is drawn again on a white background, and this phenomenon could be repeated many times. .

Example 8 15 parts of wet-process finely-divided silica (trade name: Nip Seal E-1011, manufactured by Nippon Silica Industry Co., Ltd.) was applied to the entire surface of a pink alien resin molded with ABS resin as a support.
Aqueous carboxylated NBR emulsion [trade name: Luckstar DM401, manufactured by Dainippon Ink Co., Ltd., solid content 4]
0%] 40 parts, blue pigment (trade name: Sundai Super Blue GLL, manufactured by Sanyo Dyeing Co., Ltd.) 1 part, water 20 parts, isopropyl alcohol 20 parts, silicone antifoaming agent 0.5
Parts, and 3 parts of a cross-linking agent for water-based ink, spray-coated with a blue water-based spray ink obtained by uniformly mixing and stirring.
After drying and curing at 30 ° C. for 30 minutes, a porous layer was formed to obtain a water-discolorable target.

The water discolorable target is a blue alien in a dry state due to the porous layer, and the pink color of the support is not visible. When water was attached to the water discolorable target using a water gun, the porous layer in the attached portion was changed from blue opaque to blue transparent, and changed to a purple alien mixed with pink by the lower support. . The appearance was purple when water was attached, but turned blue again when the water was evaporated and dried, and this phenomenon could be repeated many times.

[0035]

The present invention is excellent in concealing property in a dry state and transparency in a liquid absorbing state, and can realize a remarkable color change by spraying water with a water gun and other water adhering means, and also achieves a color change. Since a relatively bright color tone such as a fluorescent color can be visually recognized, it is possible to provide a water-discolorable target having high playability, which effectively functions as a target play.

[Brief description of the drawings]

FIG. 1 is an enlarged vertical cross-sectional explanatory view of one embodiment of a water-discolorable target of the present invention.

FIG. 2 is an enlarged vertical cross-sectional explanatory view of another embodiment of the water-discolorable target of the present invention.

FIG. 3 is an enlarged vertical cross-sectional explanatory view of another embodiment of the water-discolorable target of the present invention.

FIG. 4 is an enlarged vertical cross-sectional explanatory view of another embodiment of the water-discolorable target of the present invention.

FIG. 5 is an enlarged vertical cross-sectional explanatory view of another embodiment of the water-discolorable target of the present invention.

FIG. 6 is an enlarged vertical cross-sectional explanatory view of another embodiment of the water-discolorable target of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Water discoloration target 2 Support 3 Porous layer 31 Porous layer A 32 Porous layer B 4 Non-discoloring layer 5 Adhesive layer 6 Clothing 7 Hat

Claims (5)

[Claims] 1. A porous layer containing at least particulate silica and a binder resin produced by a wet method is provided on a support, and the porous layer is impregnated with water through a means for attaching water. A water-discolorable target configured to be reversibly changeable to a different aspect from the normal state. 2. The water-discolorable target according to claim 1, wherein the binder resin is a urethane-based resin. 3. The method according to claim 1, wherein the support is a fabric.
A water discolorable target as described. 4. The water discolorable target according to claim 1, which is in the form of clothing or a hat. 5. The water adhering means is spraying water by a water gun or throwing an impregnated body impregnated with water.
Any of the water discolorable targets described.