JP6618422B2 - Game toys - Google Patents

Description

  The present invention relates to a game toy. Furthermore, the present invention relates to a game toy that changes its appearance by rolling a polka dot.

Conventionally, there are many game toys that play by rolling a sphere on a support, and in particular, there are many maze games in which a guide wall is formed on a support to form a maze, and glass balls and iron balls are moved. ing.
Furthermore, as these applications, a labyrinth game is disclosed in which the user can form polka dots, thereby enhancing the fun of being able to freely select the size and number of spheres (for example, Patent Documents 1 to 3). reference).

Japanese Utility Model Publication No. 60-7110 Japanese Utility Model Publication No. 7-24380 JP 2011-206238 A

  In the maze game, the surface of the support body is subjected to water repellent treatment using a hydrophobic member subjected to flocking or water flipping sand, so that the liquid hung on the support body becomes a polka dot state, and has a desired size and number. Since a sphere can be formed, it is not only a single play like a conventional ready-made toy, but also an interesting thing that a user can arrange how to play.

  The present invention provides a game toy that can be played for a long period of time without getting tired of the user by further applying the toy using the polka dots to a more interesting configuration.

According to the present invention, a water repellent layer that makes a placed liquid polka dot is provided on the surface of a support body having a frame portion having a height formed on substantially the entire circumference, and an upper surface of the water repellent layer and / or A requirement is a game toy that is provided with a color changing portion that changes color when a polka dot comes into contact with the water repellent layer on the support.
Furthermore, the discoloration part is a discoloration layer composed of a thermochromic layer and / or a porous layer, and the thermochromic layer comprises (a) an electron donating color-forming organic compound, and (b) an electron accepting layer. A reversible thermochromic layer comprising a microcapsule pigment encapsulating at least a reversible thermochromic composition comprising a functional compound and (c) a reaction medium that controls the color reaction of (i) and (b) above, The porous layer is a layer in which a low refractive index pigment is fixed to a binder resin in a dispersed state.
Furthermore, a thermochromic layer containing a microcapsule pigment containing a reversible thermochromic composition and a binder resin is provided on the surface of the support on which the frame portion having a height is formed on substantially the entire circumference, and is placed. A requirement is a game toy in which a water-repellent layer in which the liquid is in a polka dot state is further laminated.
Further, the water repellent layer is a layer in which hydrophobic silica is fixed in a dispersed state in an organic solvent-soluble resin, an image is formed on the surface of the support, and a guide wall is formed on the surface of the support. It is required that a water repellent layer be provided on the inner peripheral surface of the frame portion.
Furthermore, it is a requirement to be a container combined game toy that constitutes a part of a box-shaped package.

According to the present invention, by placing a liquid on the support by the user, a polka dot of a desired size and number can be formed, and the support is caused to change its appearance as the polka dot rolls on the support. The game toy is an interesting game toy that users can arrange how to play.
In particular, by using a water-repellent layer in which hydrophobic silica is fixed in a dispersed state in an organic solvent-soluble resin, various laminating methods are used, and further, discoloration of the discolored portion is facilitated. A game with a variety of configurations can be realized, and it becomes more interesting.

It is explanatory drawing which shows the Example of the game toy of this invention. It is explanatory drawing which shows the use condition of the game toy of FIG. It is a principal part longitudinal cross-sectional view of the game toy of FIG. It is a principal part longitudinal cross-sectional view of the other Example of the game toy of this invention. It is explanatory drawing which shows the other Example of the game toy of this invention. It is a principal part longitudinal cross-sectional view of the other Example of the game toy of this invention.

  In the game toy, a water repellent layer is formed on the surface of the support, and a reversible thermochromic layer or a low refractive index pigment containing a microcapsule pigment encapsulating the reversible thermochromic composition in at least a part of the support. It is a game toy that is provided with a discolored portion composed of a porous layer fixed in a dispersed state on a resin, and that allows various play by the rolling of polka dots.

The support body of the game toy is not particularly limited as long as it is a material capable of forming a water repellent layer or a color changing portion. For example, paper, synthetic paper, plastic film (sheet), knitted fabric, woven fabric, non-woven fabric, etc. Fabric, synthetic leather, leather, plastic (molded article), metal, glass, ceramics, wood, stone and the like.
The shape of the support is not particularly limited, and may be a shape having a curved surface or unevenness in addition to a planar shape and a sheet shape.
The support may be provided with an arbitrary image or color portion (colored layer containing a colorant), and a regulating wall or a hole made of uneven portions.

It is preferable that a frame portion having a height that does not allow the polka dots to get over the outer periphery of the support is formed on the entire circumference. The substantially entire circumference includes a partly cut portion, and is formed in accordance with the form of the game, such as inserting and removing polka dots from the cut portion.
The shape, thickness and height of the frame are arbitrarily set according to the game form.

As the water repellent layer, conventionally disclosed water repellent materials can be used. For example, water-repellent materials such as fluororesins, paraffin resins, silicone resins, epoxy resins, etc. that have a water-repellent effect are formed directly on the support by means of printing, spray coating, sticking, dipping, etc. May be mixed with the support material to form a water-repellent support, or a support made of a hydrophobic member subjected to flocking treatment or water repellent sand may be formed on the support.
In particular, as a water-repellent layer, a layer in which hydrophobic silica is fixed in a dispersed state in an organic solvent-soluble resin has a high water-repellent effect, and the effect is permanently exhibited, and various lamination methods can be used. It is preferably used because of its high workability such as easy discoloration of the discolored portion. Therefore, it is possible to realize a game toy that is rich in variations and has a more interesting structure.

The hydrophobic silica will be described in detail.
Silica is classified into a dry method and a wet method depending on the production method, both of which have a structure in which silanol groups are arranged on the surface, and hydrophobic silica is a silane such as methylchlorosilane, polydimethylsiloxane, etc. on the silanol group. The siloxane, hexamethyldisilazane and the like are reacted to change the hydrophilicity of the silanol group to hydrophobic, so that it cannot absorb water but also exhibits water repellency.
As general-purpose hydrophobic silica, trade names Nippil SS-10, SS-20, SS-70, SS-40, SS-50, SS-50, SS-100, Nippon Aerosil Co., Ltd. manufactured by Tosoh Silica Co., Ltd. Product names AEROSIL R972, RY50, R812, R805, RX200, RY200, trade names TS-530, TS-610, TS-720, manufactured by Degussa Japan Co., Ltd. Names AEROSIL R202, R805, R812, trade names REOLOSIL MT-10, DM-10, DM-20S made by Tokuyama Corporation, trade names SYLOPHOBIC100, 200, 704, made by Fuji Silysia Chemical Co., Ltd. 4004, 507, 702, 505, 603, and the like. The hydrophobic silica has a refractive index in the range of 1.4 to 1.8.
The particle diameter of the hydrophobic silica is not particularly limited, but 0.03 to 10.0 μm is preferably used. The particle size is measured by a laser diffraction / light scattering type particle size distribution measuring device (LA-300 manufactured by Horiba, Ltd.) or a dynamic light scattering type particle size distribution measuring device (SZ-100 manufactured by Horiba, Ltd.).
In addition, 2 or more types of the said hydrophobic silica can also be used together.

The hydrophobic silica is dispersed in a solvent containing an organic solvent-soluble resin to prepare a liquid material such as paint or printing ink, and printing methods such as screen printing, offset printing, gravure printing, coater, tampo printing, transfer, etc. The surface of the support is provided with a water repellent layer by methods such as brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, and dip coating.
The hydrophobic silica is dispersed in an organic solvent because it is difficult to disperse in an aqueous emulsion as well as in an aqueous emulsion.
The organic solvent-soluble resin is dissolved or dispersed in an organic solvent, and a water-repellent layer is obtained by coating or drying a liquid composition containing hydrophobic silica entirely or partially on a support.
The organic solvent-soluble resin is a resin that dissolves at 5% by weight or more with respect to the organic solvent at 30 ° C.

  Examples of the organic solvent include n-paraffin solvents, isoparaffin solvents, naphthene solvents, aromatic solvents, α-olefin solvents and other petroleum solvents, light oil, spindle oil, machine oil, cylinder oil, turpentine oil, Examples include mineral spirit, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, propyl acetate, butyl acetate, ethyl lactate, xylene, toluene, ethanol, isopropyl alcohol, butanol and the like.

Examples of the organic solvent-soluble resin include urethane resin, acrylic ester resin, acrylic ester copolymer resin, acrylic polyol resin, vinyl chloride-vinyl acetate copolymer resin, maleic acid resin, polyester resin, styrene resin, styrene copolymer. Resin, polycarbonate resin, epoxy resin, styrene-butadiene copolymer resin, acrylonitrile-butadiene copolymer resin, methyl methacrylate-butadiene copolymer resin, butadiene resin, chloroprene resin, melamine resin, casein, starch, polyvinyl alcohol, urea resin, Acrylic resins, polyester resins, alkyd resins, styrene resins, nylon resins, vinyl acetate resins, vinyl chloride resins, acrylonitrile-butadiene-styrene copolymer resins, phenol resins, etc. Loin resins.
The mixing ratio of the hydrophobic silica and the organic solvent-soluble resin depends on the type and properties of the hydrophobic silica, preferably 2 to 5 parts by mass of the resin solid content with respect to 1 part by mass of the hydrophobic silica. More preferably, it is 2-3.5 mass parts. When the resin solid content is less than 2 parts by mass with respect to 1 part by mass of hydrophobic silica, it is difficult to obtain a practical film strength of the formed water-repellent layer. Since there is no change in the film strength of the water layer, no more is required.
In particular, when the water-repellent layer is exposed, it is preferable to increase the scratch resistance of the formed water-repellent layer (film). Therefore, the scratch resistance can be increased by using a nylon resin, a urethane resin, or an acrylic resin. It is preferable to increase.
Examples of the urethane resin include a polyester urethane resin, a polycarbonate urethane resin, and a polyether urethane resin, and two or more of them can be used in combination.
The urethane resin can be used alone, but other binder resins can be used in combination depending on the type of support and the performance required for the coating.
In the organic solvent-soluble resin, the crosslinkable resin can be further improved in film strength by adding an arbitrary crosslinking agent and crosslinking.
The water repellent layer can contain a colorant.

As the color changing portion formed on the support so as to be juxtaposed with and / or laminated with the water repellent layer, any material or configuration that changes color when polka dots come into contact may be used. However, those using the temperature of the contacted polka dots or those using a refractive index that becomes transparent when the polka dots are attached are preferable, and a discoloration layer composed of a thermochromic layer or a porous layer is useful. It is.
Furthermore, in order to improve the convenience as a game, it is preferable to use a reversible material so that repeated discoloration (mode change) is possible.

In the thermochromic layer, an inorganic material such as Ag ₂ HgI ₄ or Cu ₂ HgI ₄ , a liquid crystal, an electron-donating color-forming organic compound, an electron-accepting compound, and a color reaction between the two reversibly occur. A heat-decolorable reversible thermochromic material containing three components with the organic compound medium to be used, or a heat-developable reversible thermochromic material is used. (B) a reversible thermal discoloration comprising a microcapsule pigment including a reversible thermochromic composition comprising at least an electron accepting compound and (c) a reaction medium for controlling the color reaction of (a) and (b) above. The layer is suitable because of its high stability over time. If necessary, a binder resin described below can be used as a fixing material.

  Examples of the reversible thermochromic composition include those described in Japanese Patent Publication No. 51-44706, Japanese Patent Publication No. 51-44707, Japanese Patent Publication No. 1-29398, etc., at a predetermined temperature (discoloration point). Discolored before and after, decolored state in the temperature range above the high temperature side discoloration point, color development state in the temperature range below the low temperature side discoloration point, only one specific state exists in the normal temperature range among the two states, The other state is maintained as long as the heat or cold required to develop the state is applied, but when the heat or cold is no longer applied, the hysteresis width returns to the state exhibited in the normal temperature range. A reversible thermochromic composition of a heat decoloring type (decolored by heating and colored by cooling) having relatively small characteristics (ΔH = 1 to 7 ° C.) can be applied.

In addition, large hysteresis characteristics (ΔH _B = 8 to 50 ° C.) described in JP- _B -4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, and the like. ), That is, when the shape of the curve plotting the change in the color density due to the temperature change is lowering the temperature from the lower temperature side than the color changing temperature range, as opposed to increasing the temperature from the lower temperature side. In the specific temperature range, the color changes in a low temperature range below the complete color development temperature (t ₁ ) or the color erase state in the high temperature range above the complete color erase temperature (T ₄ ). A reversible thermochromic composition having a color memory property in a temperature range between T _{2 and} T ₃ (substantially two-phase holding temperature range) (decolored by heating and developed by cooling). Is also applicable.

The hysteresis characteristic in the color density-temperature curve of the reversible thermochromic composition will be described. For example, in FIG. 1 described in JP-A-8-39936, the vertical axis represents color density and the horizontal axis represents temperature. The change in color density due to the temperature change proceeds along the arrow. Here, A is a point indicating a density at a temperature T ₄ (hereinafter referred to as a complete decoloring temperature) that reaches a completely decolored state, and B is a temperature T ₃ (hereinafter referred to as a decoloring start temperature) that starts decoloring. C represents a density at a temperature T ₂ at which color development starts (hereinafter referred to as a color development start temperature), and D represents a temperature T ₁ at which a complete color development state is reached (hereinafter referred to as a complete color development state). This is a point indicating a density at a color development temperature).
Discoloration temperature region is a temperature region between the T ₁ and T _4, may exhibit any of the states of the colored state and the decolored state, between T ₂ and T ₃ is a large area of the difference in color density The temperature range is substantially the discoloration temperature range.
The length of the line segment EF is a scale indicating the discoloration contrast, and the length of the line segment HG passing through the midpoint of the line segment EF is a temperature width indicating the degree of hysteresis (hereinafter referred to as hysteresis width ΔH). If this ΔH value is small, only one specific state can exist in the normal temperature range among both states before and after the color change. Further, when the ΔH value is large, it is easy to maintain each state before and after the color change.

Hereinafter, the components (a), (b) and (c) of the reversible thermochromic composition will be described.
Examples of the electron donating color-forming organic compound as component (a) of the present invention include diphenylmethane phthalides, phenyl indolyl phthalides, indolyl phthalides, diphenyl methane azaphthalides, and phenyl indolyl azaphthalides. Fluoranes, styrinoquinolines, diazarhodamine lactones, pyridines, quinazolines, bisquinazolines and the like.
Examples of these compounds are given below.
3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide,
3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide,
3,3-bis (1-n-butyl-2-methylindol-3-yl) phthalide,
3,3-bis (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide,
3- [2-ethoxy-4- (N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide,
3,6-diphenylaminofluorane,
3,6-dimethoxyfluorane,
3,6-di-n-butoxyfluorane,
2-methyl-6- (N-ethyl-Np-tolylamino) fluorane,
3-chloro-6-cyclohexylaminofluorane,
2-methyl-6-cyclohexylaminofluorane,
2- (2-chloroamino) -6-dibutylaminofluorane,
2- (2-chloroanilino) -6-di-n-butylaminofluorane,
2- (3-trifluoromethylanilino) -6-diethylaminofluorane,
2- (N-methylanilino) -6- (N-ethyl-Np-tolylamino) fluorane,
1,3-dimethyl-6-diethylaminofluorane,
2-chloro-3-methyl-6-diethylaminofluorane,
2-anilino-3-methyl-6-diethylaminofluorane,
2-anilino-3-methyl-6-di-n-butylaminofluorane,
2-xylidino-3-methyl-6-diethylaminofluorane,
1,2-benz-6-diethylaminofluorane,
1,2-benz-6- (N-ethyl-N-isobutylamino) fluorane,
1,2-benz-6- (N-ethyl-N-isoamylamino) fluorane,
2- (3-methoxy-4-dodecoxystyryl) quinoline,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1 '(3'H) isobenzofuran] -3'-one,
2- (diethylamino) -8- (diethylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-g) pyrimidine-5,1 ′ (3′H) isobenzofuran] -3-one,
2- (Di-n-butylamino) -8- (di-n-butylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-g) pyrimidine-5,1 '(3' H) Isobenzofuran] -3-one,
2- (Di-n-butylamino) -8- (diethylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) isobenzofuran] -3-one,
2- (Di-n-butylamino) -8- (N-ethyl-Ni-amylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-g) pyrimidine-5,1 ' (3′H) isobenzofuran] -3-one,
2- (Dibutylamino) -8- (dipentylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3 -On,
3- (2-methoxy-4-dimethylaminophenyl) -3- (1-butyl-2-methylindol-3-yl) -4,5,6,7-tetrachlorophthalide,
3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4,5,6,7-tetrachlorophthalide,
3- (2-ethoxy-4-diethylaminophenyl) -3- (1-pentyl-2-methylindol-3-yl) -4,5,6,7-tetrachlorophthalide,
4,5,6,7-Tetrachloro-3- [4- (dimethylamino) -2-methylphenyl] -3- (1-ethyl-2-methyl-1H-indol-3-yl) -1 (3H ) -Isobenzofuranone,
3 ', 6'-bis [phenyl (2-methylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9'-[9H] xanthen] -3-one,
3 ', 6'-bis [phenyl (3-methylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9'-[9H] xanthen] -3-one,
3 ', 6'-bis [phenyl (3-ethylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9'-[9H] xanthen] -3-one,
4- [2,6-bis (2-ethoxyphenyl) -4-pyridinyl] -N, N-dimethylbenzenamine,
2- (4'-dimethylaminophenyl) -4-methoxy-quinazoline,
4,4 '-(ethylenedioxy) -bis [2- (4-diethylaminophenyl) quinazoline] and the like.
In addition to the above compounds having a substituent in the phenyl group forming the xanthene ring, the fluoranes include a substituent in the phenyl group forming the lactone ring as well as the phenyl group forming the xanthene ring (for example, And a compound having an alkyl group such as a methyl group or a halogen atom such as a chloro group.

As the electron-accepting compound of the component (b), a compound group having active protons, a pseudo-acidic compound group (a compound group that is not an acid but acts as an acid in the composition to cause the component (I) to develop color), There is a group of compounds having electron vacancies.
Examples of compounds having active protons include monophenols to polyphenols as compounds having phenolic hydroxyl groups, and alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, carboxy groups and esters thereof as substituents. Alternatively, those having an amide group, a halogen group, etc., and bis-type and tris-type phenols, phenol-aldehyde condensation resins and the like can be mentioned. Moreover, the metal salt of the compound which has the said phenolic hydroxyl group may be sufficient.
Specific examples are given below.
Phenol, o-cresol, tertiary butylcatechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, n-butyl p-hydroxybenzoate N-octyl p-hydroxybenzoate, resorcin, dodecyl gallate, 2,2-bis (4-hydroxyphenyl) propane, 4,4-dihydroxydiphenylsulfone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4 -Hydroxyphenyl) -3-methylbu 1,1-bis (4-hydroxyphenyl) -2-methylpropane, 1,1-bis (4-hydroxyphenyl) n-hexane, 1,1-bis (4-hydroxyphenyl) n-heptane, , 1-bis (4-hydroxyphenyl) n-octane, 1,1-bis (4-hydroxyphenyl) n-nonane, 1,1-bis (4-hydroxyphenyl) n-decane, 1,1-bis ( 4-hydroxyphenyl) n-dodecane, 1,1-bis (4-hydroxyphenyl) 2-ethylhexane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) ethyl Propionate, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2 Bis (4-hydroxyphenyl) n- heptane, there is 2,2-bis (4-hydroxyphenyl) n- nonane.
The compound having a phenolic hydroxyl group can develop the most effective thermochromic property, but aromatic carboxylic acids and aliphatic carboxylic acids having 2 to 5 carbon atoms, carboxylic acid metal salts, acidic phosphate esters and their It may be a compound selected from metal salts, 1,2,3-triazole and derivatives thereof.

The component (c) of the reaction medium that causes the electron transfer reaction by the components (a) and (b) to occur reversibly in a specific temperature range will be described.
Examples of the component (c) include alcohols, esters, ketones, and ethers.
The said compound is illustrated below.
As the alcohols, aliphatic monovalent saturated alcohols having 10 or more carbon atoms are effective. Specifically, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl Alcohol, heptadecyl alcohol, octadecyl alcohol, eicosyl alcohol, docosyl alcohol, etc. are mentioned.

As the esters, esters having 10 or more carbon atoms are effective, and any combination of a monovalent carboxylic acid having an aliphatic and alicyclic or aromatic ring and a monohydric alcohol having an aliphatic and alicyclic or aromatic ring. Esters, aliphatic and alicyclic rings obtained from any combination of esters, aliphatic and alicyclic or aromatic polyvalent carboxylic acids obtained from the above and monohydric alcohols having aliphatic and alicyclic or aromatic rings Or esters obtained from any combination of monovalent carboxylic acid having an aromatic ring and aliphatic and alicyclic or polyhydric alcohol having an aromatic ring, specifically, ethyl caprylate, octyl caprylate, capryl Stearyl acid, myristyl caprate, docosyl caprate, 2-ethylhexyl laurate, n-decyl laurate, myris 3-methylbutyl acid, cetyl myristate, isopropyl palmitate, neopentyl palmitate, nonyl palmitate, cyclohexyl palmitate, n-butyl stearate, 2-methylbutyl stearate, 3,5,5-trimethylhexyl stearate, stearin N-undecyl acid, pentadecyl stearate, stearyl stearate, cyclohexylmethyl stearate, isopropyl behenate, hexyl behenate, lauryl behenate, behenyl behenate, cetyl benzoate, stearyl p-tert-butylbenzoate, dimyristyl phthalate , Distearyl phthalate, dimyristyl oxalate, dicetyl oxalate, dicetyl malonate, dilauryl succinate, dilauryl glutarate, diundecyl adipate, azelaic acid Lauryl, di- (n-nonyl) sebacate, dineopentyl 1,18-octadecylmethylenedicarboxylate, ethylene glycol dimyristate, propylene glycol dilaurate, propylene glycol distearate, hexylene glycol dipalmitate, 1,5-pentane Diol distearate, 1,2,6-hexanetriol trimyristate, 1,4-cyclohexanediol didecyl, 1,4-cyclohexanedimethanol dimyristate, xylene glycol dicaprate, xylene glycol distearate, etc. Can be mentioned.
Further, esters of saturated fatty acids and branched fatty alcohols, unsaturated fatty acids or branched or substituted saturated fatty acids and esters of fatty alcohols having 16 or more carbon atoms, cetyl butyrate, stearyl butyrate and Ester compounds selected from behenyl butyrate are also effective.
Specifically, 2-ethylhexyl butyrate, 2-ethylhexyl behenate, 2-ethylhexyl myristate, 2-ethylhexyl caprate, 3,5,5-trimethylhexyl laurate, 3,5,5-trimethylhexyl palmitate, 3,5,5-trimethylhexyl stearate, 2-methylbutyl caproate, 2-methylbutyl caprylate, 2-methylbutyl caprate, 1-ethylpropyl palmitate, 1-ethylpropyl stearate, 1-ethylpropyl behenate, 1-ethylhexyl laurate, 1-ethylhexyl myristate, 1-ethylhexyl palmitate, 2-methylpentyl caproate, 2-methylpentyl caprylate, 2-methylpentyl caprate, 2-methylpentyl laurate, 2-stearate Mechi Butyl, 2-methylbutyl stearate, 3-methylbutyl stearate, 1-methylheptyl stearate, 2-methylbutyl behenate, 3-methylbutyl behenate, 1-methylheptyl stearate, 1-methylheptyl behenate, caproic acid 1 -Ethylpentyl, 1-ethylpentyl palmitate, 1-methylpropyl stearate, 1-methyloctyl stearate, 1-methylhexyl stearate, 1,1-dimethylpropyl laurate, 1-methylpentyl caprate, palmitic acid 2-methylhexyl, 2-methylhexyl stearate, 2-methylhexyl behenate, 3,7-dimethyloctyl laurate, 3,7-dimethyloctyl myristate, 3,7-dimethyloctyl palmitate, 3, stearate 7-Jime Ruoctyl, 3,7-dimethyloctyl behenate, stearyl oleate, behenyl oleate, stearyl linoleate, behenyl linoleate, 3,7-dimethyloctyl erucate, stearyl erucate, isostearyl erucate, cetyl isostearate, isostearic acid Examples include stearyl acid, 2-methylpentyl 12-hydroxystearate, 2-ethylhexyl 18-bromostearate, isostearyl 2-ketomyristate, 2-ethylhexyl 2-fluoromyristate, cetyl butyrate, stearyl butyrate, and behenyl butyrate. It is done.

  In addition, as the component (c) for obtaining a reversible thermochromic composition having color memory, a carboxylic acid ester compound exhibiting a ΔT value (melting point-cloud point) of 5 ° C. or more and less than 50 ° C., for example, in a molecule A carboxylic acid ester containing a substituted aromatic ring, an ester of a carboxylic acid containing an unsubstituted aromatic ring and an aliphatic alcohol having 10 or more carbon atoms, a carboxylic acid ester containing a cyclohexyl group in the molecule, a fatty acid having 6 or more carbon atoms, Unsubstituted aromatic alcohol or ester of phenol, fatty acid having 8 or more carbon atoms and branched aliphatic alcohol or ester, dicarboxylic acid and ester of aromatic alcohol or branched aliphatic alcohol, dibenzyl cinnamate, heptyl stearate, didecyl adipate , Dilauryl adipate, dimyristyl adipate, dicetyl adipate, distearate adipate , Trilaurin, trimyristin, tristearin, Dimyristate, distearate and the like are used.

Also, fatty acid ester compounds obtained from an odd aliphatic monohydric alcohol having 9 or more carbon atoms and an aliphatic carboxylic acid having an even number of carbon atoms, n-pentyl alcohol or n-heptyl alcohol and an even fat having 10 to 16 carbon atoms. A fatty acid ester compound having a total carbon number of 17 to 23 obtained from a group carboxylic acid is also effective.
Specifically, n-pentadecyl acetate, n-tridecyl butyrate, n-pentadecyl butyrate, n-undecyl caproate, n-tridecyl caproate, n-pentadecyl caproate, n-nonyl caprylate, n-undecyl caprylate, N-tridecyl caprylate, n-pentadecyl caprylate, n-heptyl caprate, n-nonyl caprate, n-undecyl caprate, n-tridecyl caprate, n-pentadecyl caprate, n-pentyl laurate, lauric acid n-heptyl, n-nonyl laurate, n-undecyl laurate, n-tridecyl laurate, n-pentadecyl laurate, n-pentyl myristate, n-heptyl myristate, n-nonyl myristate, n-myristate Undecyl, n-tridecyl myristate, N-pentadecyl ristinate, n-pentyl palmitate, n-heptyl palmitate, n-nonyl palmitate, n-undecyl palmitate, n-tridecyl palmitate, n-pentadecyl palmitate, n-nonyl stearate, stearic acid n-undecyl, n-tridecyl stearate, n-pentadecyl stearate, n-nonyl eicosanoate, n-undecyl eicosanoate, n-tridecyl eicosanoate, n-pentadecyl eicosanoate, n-nonyl behenate, n-behenate Examples include undecyl, n-tridecyl behenate, and n-pentadecyl behenate.

As the ketones, aliphatic ketones having a total carbon number of 10 or more are effective, and 2-decanone, 3-decanone, 4-decanone, 2-undecanone, 3-undecanone, 4-undecanone, 5-undecanone, 2 -Dodecanone, 3-dodecanone, 4-dodecanone, 5-dodecanone, 2-tridecanone, 3-tridecanone, 2-tetradecanone, 2-pentadecanone, 8-pentadecanone, 2-hexadecanone, 3-hexadecanone, 9-heptadecanone, 2-pentadecanone 2-octadecanone, 2-nonadecanone, 10-nonadecanone, 2-eicosanone, 11-eicosanone, 2-heneicosanone, 2-docosanone, laurone, stearone and the like.
Further, arylalkyl ketones having 12 to 24 carbon atoms in total, such as n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradecano Phenone, 4-n-dodecanacetophenone, n-tridecanophenone, 4-n-undecanoacetophenone, n-laurophenone, 4-n-decanoacetophenone, n-undecanophenone, 4-n-nonylacetophenone, n -Decanophenone, 4-n-octylacetophenone, n-nonanophenone, 4-n-heptylacetophenone, n-octanophenone, 4-n-hexylacetophenone, 4-n-cyclohexylacetophenone, 4-tert-butylpropiophenone, n-heptaphenone, 4-n-pentylacetophene Emissions, cyclohexyl phenyl ketone, benzyl -n- butyl ketone, 4-n-butyl acetophenone, n- hexanophenone, 4-isobutyl acetophenone, 1-acetonaphthone, 2-acetonaphthone, may be mentioned cyclopentyl phenyl ketone.

  As ethers, aliphatic ethers having a total carbon number of 10 or more are effective, and dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, diundecyl ether, didodecyl ether, ditridecyl ether, Decyl ether, ditetradecyl ether, dipentadecyl ether, dihexadecyl ether, dioctadecyl ether, decane diol dimethyl ether, undecane diol dimethyl ether, dodecane diol dimethyl ether, tridecane diol dimethyl ether, decane diol diethyl ether, undecane diol diethyl ether, etc. Can be mentioned.

  Further, as the electron-accepting compound, a specific alkoxyphenol compound having a linear or side chain alkyl group having 3 to 18 carbon atoms may be used (Japanese Patent Laid-Open Nos. 11-129623 and 11-5973), Hydroxybenzoic acid esters (Japanese Patent Laid-Open No. 2001-105732), gallic acid esters and the like (Japanese Patent Publication No. 51-44706, Japanese Patent Laid-Open No. 2003-253149) are used. A microcapsule pigment containing a reversible thermochromic composition that is decolored by cooling) can also be applied.

  The blending ratio of the components (A), (B), and (C) depends on the concentration, the color change temperature, the color change form, and the type of each component. In general, the component ratio at which a desired color change characteristic is obtained is as follows. (B) Component 1, (b) Component 0.1-50, preferably 0.5-20, (C) Component 1-800, preferably 5-200 (all the above ratios) Part by mass).

Methods for microencapsulating the reversible thermochromic composition include interfacial polymerization, interfacial polycondensation, in situ polymerization, in-liquid curing coating, phase separation from aqueous solution, and phase separation from organic solvent. There are a melt dispersion cooling method, an air suspension coating method, a spray drying method, and the like, which are appropriately selected according to use.
Further, a secondary resin film may be provided on the surface of the microcapsule according to the purpose to impart durability, or the surface characteristics may be modified for practical use.
Here, a non-thermochromic dye or pigment may be blended in the microcapsules so as to exhibit a tautomatic color change from colored (1) to colored (2).
By encapsulating in the microcapsule, a chemically and physically stable pigment can be formed, and an average particle size of 0.1 to 50 μm, preferably 0.5 to 30 μm, more preferably 1 to 20 μm is practical. Meet.
The particle size is measured using a laser diffraction / scattering particle size distribution measuring apparatus (manufactured by Horiba, Ltd .; LA-300), and the average particle size (median diameter) is based on volume based on the numerical value. Calculate with

The porous layer is a layer in which a low refractive index pigment is fixed in a dispersed state together with a binder resin and is opaque in a non-liquid absorbing state and transparent in a liquid absorbing state.
Examples of the low refractive index pigment include silicic acid and salts thereof, barite powder, barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, talc, alumina white, magnesium carbonate, and the like.
The low refractive index pigment has a refractive index in the range of 1.4 to 1.8, and exhibits good transparency when liquid is absorbed.
Examples of the silicic acid salt include aluminum silicate, aluminum potassium silicate, sodium aluminum silicate, aluminum calcium silicate, potassium silicate, calcium silicate, calcium sodium silicate, sodium silicate, magnesium silicate, and magnesium potassium silicate.
The particle size of the low refractive index pigment is not particularly limited, but 0.03 to 10.0 μm is preferably used.
Two or more of the low refractive index pigments can be used in combination.
In addition, silicic acid is mentioned as a low refractive index pigment used suitably.
The silicic acid may be silicic acid produced by a dry process (hereinafter referred to as dry process silicic acid), but is preferably silicic acid produced by a wet process (hereinafter referred to as wet process silicic acid).
This point will be described below.
Silicic acid is produced as amorphous amorphous silicic acid, and depending on its production method, the dry method using a gas phase reaction such as thermal decomposition of silicon halide such as silicon tetrachloride and the decomposition by acid such as sodium silicate. It is roughly classified into those by a wet method using a liquid phase reaction such as.
The dry process silicic acid and the wet process silicic acid have different structures, and the dry process silicic acid has a structure in which silicic acid is closely bound, whereas the wet process silicic acid has a structure part in which a long molecular arrangement is formed by condensation of silicic acid. have.
Therefore, wet-process silicic acid has a rougher molecular structure than dry-process silicic acid. Therefore, when wet-process silicic acid is applied to the porous layer, the diffuse reflection of light in the dry state compared to the system using dry-process silicic acid. It is presumed that the concealability in the normal state is increased.
In addition, since the porous layer absorbs water, the wet process silicic acid has more hydroxyl groups present as silanol groups on the particle surface than the dry process silicic acid, and has a high degree of hydrophilicity. It is done.
In addition, in order to adjust the concealability in the normal state of the porous layer and the transparency in the liquid absorption state, other low refractive index pigments can be used in combination with the wet method silicic acid.

Examples of the binder resin include urethane resin, nylon resin, vinyl acetate resin, acrylic ester resin, acrylic ester copolymer resin, acrylic polyol resin, vinyl chloride-vinyl acetate copolymer resin, maleic resin, polyester resin, styrene. Resin, styrene copolymer resin, polyethylene resin, polycarbonate resin, epoxy resin, styrene-butadiene copolymer resin, acrylonitrile-butadiene copolymer resin, methyl methacrylate-butadiene copolymer resin, butadiene resin, chloroprene resin, melamine resin, and the above Each resin emulsion, casein, starch, cellulose derivative, polyvinyl alcohol, urea resin, phenol resin and the like can be mentioned.
The mixing ratio of the low refractive index pigment and these binder resins depends on the type and properties of the low refractive index pigment, but preferably the binder resin solid content is 0.5 to 1 part by mass with respect to 1 part by mass of the low refractive index pigment. 2 parts by mass, and more preferably 0.8 to 1.5 parts by mass. When 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 the content exceeds 2 parts by mass. In this case, the water permeability into the porous layer is deteriorated.
Since the porous layer has a smaller mixing ratio of the binder resin to the colorant than a general coating film, it is difficult to obtain sufficient film strength. Therefore, among the binder resins, it is preferable to increase the scratch resistance using a nylon resin or a urethane resin.
Examples of the urethane resin include a polyester urethane resin, a polycarbonate urethane resin, and a polyether urethane resin, and two or more of them can be used in combination. In addition, a urethane emulsion resin in which the resin is emulsified and dispersed in water, or a colloid in which the resin is self-emulsified without the need for an emulsifier by an ionic group of the ionic urethane resin (urethane ionomer) itself and dissolved or dispersed in water. A dispersion type (ionomer type) urethane resin can also be used.
The urethane-based resin may be either an aqueous urethane-based resin or an oil-based urethane-based resin, but in the present invention, an aqueous urethane-based resin, in particular, a urethane-based emulsion resin or a colloidally dispersed urethane-based resin is suitable. Used for.
The urethane resin can be used alone, but other binder resins can be used in combination depending on the type of support and the performance required for the coating. When a binder resin other than the urethane resin is used in combination, in order to obtain a practical film strength, it is preferable to contain 30% or more of the urethane resin in a solid mass ratio in the binder resin of the porous layer.
In the binder resin, a crosslinkable resin can be further improved in film strength by adding an arbitrary crosslinking agent and crosslinking.
The binder resin has a large or small affinity with water. By combining these, the penetration time into the porous layer, the degree of penetration, and the slow speed of drying after the penetration can be adjusted. Furthermore, the said adjustment can be controlled by adding a dispersing agent suitably.
The coating amount of the porous layer is 5 to 50 g / m ² , preferably 10 to 30 g / m ² .
If it is less than 5 g / m ² , it is difficult to obtain sufficient concealability in a normal state, and if it exceeds 50 g / m ² , it is difficult to obtain sufficient transparency upon liquid absorption.

In addition, a general dye, a fluorescent dye, and a color pigment can be added to the porous layer to diversify the color change.
Examples of the color pigment include general pigments and fluorescent pigments, titanium dioxide-coated mica, iron oxide-titanium dioxide-coated mica, iron oxide-coated mica, guanine, sericite, basic lead carbonate, acidic lead arsenate, and bismuth oxychloride. A metallic luster pigment can be illustrated.
In addition, a reversible thermochromic material that reversibly changes color according to a temperature change can be mixed, and the color can be changed depending on the environmental temperature or the water temperature to be adhered.

A colored layer is provided between the color-changing layer (porous layer or thermochromic layer) and the support (that is, the lower layer of the color-changing layer), and when the porous layer is in a liquid absorption state, the thermochromic layer is decolored. It can also be configured such that the hue of the colored layer is visible when in the state.
Furthermore, a colored image (symbol layer) such as a pattern may be arranged on the upper layer of the color changing layer or a support around the color changing layer to further diversify the appearance change or improve the decorativeness of the game toy. it can. Examples of the image of the colored image (design layer) include characters, symbols, patterns and the like in addition to the design.

  Any color changing layer (porous layer or thermochromic layer), colored layer or pattern layer formed on the support may be a known means such as screen printing, offset printing, gravure printing, coater, tampo printing, transfer. Can be appropriately formed by printing means such as brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, and dip coating.

Further, in addition to the above-mentioned configuration as a game toy, when using a thermochromic layer, after providing a thermochromic layer containing a microcapsule pigment and a binder resin containing a reversible thermochromic composition on the surface of the support, Furthermore, it can also be set as the structure which laminates | stacks a water repellent layer. In this case, the above-mentioned materials can be applied to the support (including the colored layer), the thermochromic layer, and the water repellent layer.
In the game toy formed with the above configuration, the liquid placed on the water repellent layer is in a polka dot state and rolls, and the polka dot is temporarily detained due to the effect at the location where the thermochromic layer exists in the lower layer. Therefore, thermal discoloration is surely performed by the temperature of the polka dots. Therefore, it becomes a game toy that can exhibit the same aspect change as the above-described configuration.
Since the water repellent layer is laminated on the upper layer of the thermochromic layer, the above configuration can protect the thermochromic layer from ultraviolet rays, scratches, and the like, and thus is advantageous for longer-term use.

  In addition, the game toy having the above-described configurations is excellent in convenience and portability and can easily form polka dots by combining a dropper such as a dropper, spray, and cup as a set to form polka dots. It can also be a toy set.

  In addition, the game toy having the above-described configuration can be used as a container-to-game game toy by itself as a game toy or by being provided as a part of a package enclosing various products. In this case, by using an existing package as a support, added value can be given to a package that is normally discarded, so that the reusability and the sales promotion effect are high.

  Examples are shown below, but the present invention is not limited thereto. In addition, the part in an Example shows a mass part.

Example 1
Production of thermochromic game toys (see FIGS. 1 to 3)
Hydrophobic silica [product of Tosoh Silica Co., Ltd., product name nip seal SS20] 9.8 parts, vinyl chloride-vinyl acetate copolymer resin (manufactured by Nissin Chemical Industry Co., Ltd., product name Solvain C solid) as an organic solvent soluble resin 100%) 20 parts, 50 parts of cyclohexanone, and 1 part of a nonionic additive were mixed to obtain a water-repellent ink (solid ratio of hydrophobic silica and organic solvent-soluble resin, 1: 2.04).
After printing a tree and insect pattern (colored layer 3) with a commercially available laser printer on a rectangular coated paper (230 μm thick) of an arbitrary size to be the support 2, screen printing is performed using the water-repellent ink. A water repellent layer 4 was provided on the entire support. Thereafter, the four corners were cut into a 1 cm square shape.
Further, on the water-repellent layer 4, a reversible thermochromic microcapsule pigment encapsulating a heat erasable reversible thermochromic composition having a color memory property that changes color from blue to colorless [average particle size 8 μm, complete color development] Temperature 15 ° C., complete decoloring temperature 30 ° C.] 30 parts, pink fluorescent pigment 0.5 part, urethane emulsion resin 61.5 parts, thickener 2 parts, leveling agent 0.5 part, antifoaming agent 0. Reversible thermochromic ink A comprising 5 parts and 5 parts of a crosslinking agent, and a reversible thermochromic microcapsule encapsulating a heat decoloring reversible thermochromic composition having color memory that changes from orange to colorless. 30.5 parts of pigment (average particle size 8 μm, complete color developing temperature 15 ° C., complete color erasing temperature 30 ° C.), 61.5 parts urethane emulsion resin, 2 parts thickener, 0.5 part leveling agent, defoaming agent Reversible thermal transformation consisting of 0.5 parts and 5 parts of cross-linking agent Reversible thermochromic microcapsule pigment encapsulating chromatic ink B and a heat-erasable reversible thermochromic composition having color memory that changes from red to colorless [average particle size 8 μm, complete color temperature 15 ° C. , Complete decoloring temperature 30 ° C.] 30.5 parts, urethane emulsion resin 61.5 parts, thickener 2 parts, leveling agent 0.5 part, antifoaming agent 0.5 part, crosslinking agent 5 parts reversible Using a thermochromic ink C, printing was performed at a plurality of locations in a circular shape on a 120-mesh screen plate to form a reversible thermochromic layer (color-changing layer 5) to obtain a reversible thermochromic sheet.
Furthermore, the game toy 1 of reversible thermochromic property was obtained by bending 1 cm each of the four sides of the support 1 vertically to form the frame portion 6.

In the game toy 1, since the polka dots 7 are formed by dripping the liquid in the frame, the size and number thereof can be freely determined by the user, and are formed by tilting the support 2. The polka dots 7 roll on the support (water repellent layer surface). By using water whose temperature is lower than 15 ° C. (for example, using cold water of 10 ° C.), when the rolling polka dots 7 pass over each discoloration layer 5, the color changes from pink to purple (5A ) And the ones that appear orange or red (5BC) appearing visually, and the toy can enjoy the change of appearance that the fruit ripens and bears fruit.
The aspect change can be repeatedly performed by a temperature change, and after use, it is returned to its original state by being exposed to 30 ° C. or higher, so that it can be used repeatedly and has an interesting configuration.

Example 2
Production of water discoloration game toys (see Fig. 4)
2 parts of hydrophobic silica [product name Nipseal SS50A, manufactured by Tosoh Silica Co., Ltd.], 10 parts of a solvent-type fluororesin (product of DIC Corporation, product name: Defensor TR-101, solid content 31%) as an organic solvent-soluble resin , 2 parts of cyclohexanone, 2 parts of isocyanate-based curing agent (manufactured by DIC Corporation, product name Vernock DN-950 solid content 75%) and 1 part of nonionic additive were mixed to obtain water-repellent ink (hydrophobic silica And solid ratio of organic solvent soluble resin, 1: 2.3).
A water repellent layer 4 is formed on the support by screen printing on a 100 μm-thick red transparent polyethylene terephthalate film as the support 2 using a plate in which a plurality of rounded patterns are randomly scattered using the water-repellent ink. Was established.
Further, on the water-repellent layer, 15 parts of wet-process fine powder silica [trade name: NIPSEAL E-200, manufactured by Nippon Silica Industry Co., Ltd.], urethane emulsion [trade name: Hydran HW-930, Dainippon Ink & Chemicals, Inc.] Co., Ltd., solid content 50%] 30 parts, 50 parts of water, 0.5 parts of silicone-based antifoaming agent, 3 parts of thickener for water-based ink, 1 part of ethylene glycol, 3 parts of blocked isocyanate-based crosslinking agent Using a white screen-printing ink mixed and stirred in a 80-mesh screen plate, printing is performed on a plurality of round punched portions where a water-repellent layer is not formed, followed by drying and curing to form a porous layer A reversible water color-changing sheet was obtained by forming (color-changing layer 5).
Furthermore, 1 cm each of the four sides of the support 1 was bent vertically to form a frame portion 6, thereby obtaining a reversible water discoloring game toy 1 having a white surface as a whole.

In the game toy 1, since the polka dots 7 are formed by dripping the liquid on the white surface in the frame, the size and number can be freely determined by the user, and the support 2 is tilted. The formed polka dots 7 roll on the support. On the surface (round portion) of the porous layer 5 through which the rolling polka dots 7 pass, the porous layer 5 becomes transparent and the lower red transparent portion appears, so that the red round transmissive portion appears from the white surface. As it was put out, the back of the part was seen through.
The aspect change can be repeatedly performed by adhering the liquid and drying it, resulting in an interesting composition.

Example 3
Production of thermochromic game toy Hydrophobic silica [manufactured by Tosoh Silica Co., Ltd., product name nip seal SS50A] 2.3 parts, blue pigment (manufactured by Clariant Co., Ltd., product name HOSTAPERM BLUE B2G) 0.05 parts, organic As a solvent-soluble resin, 10 parts of a solvent-type acrylic resin (manufactured by DIC Corporation, product name: Acrydic A-801-P solid content: 50%) and 20 parts of butyl acetate were mixed to obtain a water-repellent ink (hydrophobic silica And solid ratio of organic solvent soluble resin, 1: 2.2).
Molded product in maze form (guide wall protruding from the plane, outer peripheral wall lacking a part to serve as a water inlet, and a plurality of hemispherical recesses recessed from the plane) obtained by molding white ABS resin as the support 2 The water repellent layer 4 was provided on the entire surface of the film by spray coating using the water repellent ink.
Further, on the water-repellent layer of the hemispherical concave portion, a reversible thermochromic microcapsule pigment having an average color particle size of 8 μm encapsulating a heat decoloring reversible thermochromic composition having a color memory property that changes from red to colorless. , Complete color development temperature 15 ° C., complete color erasing temperature 30 ° C.] 4.0 parts are dispersed in an oil vehicle containing a binder resin and sprayed with an oil spray ink, and a reversible thermochromic layer (discoloration layer 5) A reversible thermochromic support was obtained.
Further, by covering the outer peripheral wall of the support 2 with a transparent resin plate, a reversible thermochromic maze game toy 1 was obtained.

In the game toy 1, since the polka dots 7 are formed by injecting liquid from the water inlet, the size and number can be freely determined by the user and formed by tilting the support 2. The constructed polka dots 7 roll on the support. When water having a temperature of less than 15 ° C. is used (for example, 10 ° C. cold water is used), the rolling polka dots 7 fall into the respective hemispherical recesses (discoloration layer 5), thereby changing from colorless to red. It became clear that the change was visually recognized and caught by the obstacle, and it became a maze toy that can be enjoyed more by using the aspect change.
The aspect change can be repeatedly performed by a temperature change, and after use, it is returned to its original state by being exposed to 30 ° C. or higher, so that it can be used repeatedly and has an interesting configuration.

Example 4 (see FIG. 5)
Production of a box-type thermochromic game toy A surface having approximately the same size as the image printing portion is added to the support 2 of the first embodiment so as to be a lid portion 81 (including an insertion piece 82). A thermochromic sheet was obtained by providing the colored layer 3, the water-repellent layer 4 and the color-changing layer 5 with the same configuration as in Example 1 except that the height of 6 was set to 3 cm.
Further, four sides of the support body 2 (one of which is provided with a lid portion 81) are bent vertically by 3 cm to form the frame portion 6, and further, the surface to be the lid portion 81 is further bent (the insertion piece 82 is also bent) to form a box shape. A reversible thermochromic game toy 1 (container combined game toy) in the form of a container 8 was obtained.
In the above-described configuration, the same play as in Example 1 can be performed, and the box-like container 8 can be used as a product package, so that the sales promotion effect is high.

Example 5
Production of thermochromic game toys (see FIGS. 1, 2 and 6)
Reversible thermochromic microcapsule pigment encapsulating a heat erasable reversible thermochromic composition having color memory that changes from blue to colorless [average particle diameter 8 μm, complete color developing temperature 5 ° C., complete color erasing temperature 10 ° C. ] Reversible consisting of 30 parts, pink fluorescent pigment 0.5 part, urethane emulsion resin 61.5 parts, thickener 2 parts, leveling agent 0.5 part, antifoaming agent 0.5 part, and crosslinking agent 5 parts Thermochromic ink A and reversible thermochromic microcapsule pigment encapsulating a heat erasable reversible thermochromic composition having color memory that changes from orange to colorless [average particle size 8 μm, complete color temperature 5 ° C, complete decoloring temperature 10 ° C] 30.5 parts, urethane emulsion resin 61.5 parts, thickener 2 parts, leveling agent 0.5 parts, antifoaming agent 0.5 parts, crosslinking agent 5 parts From reversible thermochromic ink B and red Reversible thermochromic microcapsule pigment encapsulating a heat erasable reversible thermochromic composition having a color memory property that changes colorlessly [average particle size 8 μm, complete color developing temperature 5 ° C., complete color erasing temperature 10 ° C.] 30 Reversible thermochromic ink C comprising 5 parts, 61.5 parts of urethane emulsion resin, 2 parts of thickener, 0.5 part of leveling agent, 0.5 part of antifoaming agent and 5 parts of crosslinking agent was obtained.
After printing a tree and insect pattern (colored layer 3) with a commercially available laser printer on a rectangular coated paper (230 μm thick) of an arbitrary size to be the support 2, the reversible thermochromic inks A to C are used. A reversible thermochromic layer (color-changing layer 5) was formed by printing a plurality of positions in a circular shape on a 120-mesh screen plate.
Further, 9.8 parts of hydrophobic silica (product name Nip Seal SS20, manufactured by Tosoh Silica Co., Ltd.) on the entire surface of the support provided with the color changing layer 5, vinyl chloride-vinyl acetate copolymer resin as an organic solvent-soluble resin. (Nissin Chemical Industry Co., Ltd., product name Solvain C 100% solid content) 20 parts, 50 parts cyclohexanone and 1 part nonionic additive were mixed to form a water repellent ink (solid form of hydrophobic silica and organic solvent soluble resin). The water repellent layer 4 was provided by screen printing using a ratio of 1: 2.04).
Thereafter, the four corners were cut into a 1 cm square shape, and 1 cm each of the four sides of the support 1 was bent vertically to form a frame portion 6, thereby obtaining a reversible thermochromic game toy 1.

In the game toy 1, since the polka dots 7 are formed by dripping the liquid in the frame, the size and number thereof can be freely determined by the user, and are formed by tilting the support 2. The polka dots 7 roll on the support (water repellent layer surface). By using water having a temperature of less than 15 ° C. (for example, using cold water of 3 ° C.), the rolling polka dots 7 are temporarily fixed when passing over each discoloration layer 5 and change from pink to purple. The thing (5A) and the thing (5BC) from which colorless or orange or red appears were visually recognized, and it became a toy which can enjoy the aspect change that a fruit ripens and bears fruit. Furthermore, the polka dots fixed by inclining were rolling.
The aspect change can be repeatedly performed by a temperature change, and after use, it is returned to its original state by being exposed to 10 ° C. or more, so that it can be used repeatedly and has an interesting configuration.

1 game toy 2 support 3 colored layer (design)
4 Water repellent layer 5 Discolored layer (reversible thermochromic layer, porous layer)
5A Discolored layer in a discolored state 5BC Discolored layer in a colored state 6 Frame portion 7 Polka dot 8 Box-shaped container 81 Lid portion 82 Plug-in piece

Claims (10)

  A water-repellent layer is provided on the surface of the support in which a frame portion having a height is formed on substantially the entire circumference, and the placed liquid is in a polka dot state, and the upper surface of the water-repellent layer and / or on the support A game toy comprising a discoloration portion that discolors when a polka dot comes into contact with the water repellent layer.   The game toy according to claim 1, wherein the discoloration portion is a discoloration layer composed of a thermochromic layer and / or a porous layer.   The thermochromic layer comprises (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction medium that controls the color reaction of (a) and (b). The game toy according to claim 2, which is a reversible thermochromic layer containing a microcapsule pigment encapsulating at least a reversible thermochromic composition.   The game toy according to claim 2, wherein the porous layer is a layer in which a low refractive index pigment is fixed to a binder resin in a dispersed state.   A thermochromic layer containing a microcapsule pigment enclosing a reversible thermochromic composition and a binder resin is provided on the surface of a support having a frame portion having a height formed on almost the entire circumference. A game toy in which a water-repellent layer in a polka dot state is further laminated.   The game toy according to claim 1, wherein the water repellent layer is a layer in which hydrophobic silica is fixed in a dispersed state in an organic solvent-soluble resin.   The game toy according to any one of claims 1 to 6, wherein an image is formed on a surface of the support.   The game toy according to claim 1, wherein a guide wall is formed on a surface of the support body.   The game toy according to any one of claims 1 to 8, wherein a water repellent layer is provided on an inner peripheral surface of the frame portion.   The game toy according to any one of claims 1 to 9, wherein the game toy is a container-use game toy constituting a part of a box-shaped package.