JP2001149666A - Reversibly heat-discoloring three-dimensional object - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reversibly heat-discoloring three-dimensional object being simple, excellent in merchandise property, and having its internal structure rendered visible or invisible depending on temperature changes. SOLUTION: The reversibly heat-discoloring three-dimensional object 1 has on the surface of a three-dimensional object 2 an internal structure print layer 3 drawn by shading method to show the internal structure of the three- dimensional object, and a reversibly color discoloring layer 4 rendering the internal structure print layer reversibly visible and invisible depending on temperature changes.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a reversible thermochromic three-dimensional object. More specifically, the present invention relates to a reversible thermochromic three-dimensional object in which the internal structure of the three-dimensional object is reversibly hidden by a change in temperature.

[0002]

2. Description of the Related Art Hitherto, there has been disclosed a configuration in which a reversible thermochromic layer is provided on the surface of a three-dimensional object to conceal the inside (Japanese Patent Application Laid-Open No. Hei 6 (1994)).
-135144). The conventional internal concealed three-dimensional object as described above can make the inside visible or invisible by a change in temperature, and in particular, an internal structure related to the form of the three-dimensional object is concealed by a change in temperature. The internally concealed three-dimensional object thus configured has unexpectedness and excellent merchantability, and can be suitably used in the toy field, decoration field, and the like. However, the three-dimensional object requires a built-in internal structure to be built in the three-dimensional object, which causes troubles and costs.

[0003]

The inventor of the present invention has made extensive studies on a reversible thermochromic three-dimensional object capable of reversibly concealing the internal structure of the three-dimensional object. The present inventors have found that the above problems can be solved by forming the internal structure as a printing layer drawn by a shadow painting method, and completed the present invention.

[0004]

SUMMARY OF THE INVENTION The present invention provides an internal structure printing layer drawn on a surface of a three-dimensional object by a shading method showing the internal structure of the three-dimensional object, and the inner structure printing layer is reversibly changed by a temperature change. And a reversible thermochromic three-dimensional object provided with a reversible thermochromic layer invisible to the user.

The present invention will be described in more detail. Examples of the three-dimensional object include toys imitating dolls, animals, vehicles, buildings, plants, foods and the like. Examples of the material forming the three-dimensional object include resin, glass, metal, ceramics, wood, and stone, and a thermoplastic resin or a thermosetting resin is preferably used.

[0006] The three-dimensional object is provided with a printing layer imitating the internal structure of the three-dimensional object related to the form of the three-dimensional object, and the printing layer is shaded by shading of color to represent a three-dimensional effect. It is an image printed by a so-called shadow painting method, and can show a state in which the internal structure of the three-dimensional object is enclosed inside the three-dimensional object. Regarding the formation of the printing layer, printing is performed by an appropriate method using a general-purpose general ink. Further, the printing layer is not limited to the one directly formed on the surface of the three-dimensional object. The configuration may be as follows.
A specific example of the three-dimensional object and the print layer is a configuration in which a print layer in which an image of the engine form of the automobile is drawn by a shadow image method is provided on a bonnet portion of the three-dimensional object imitating the form of an automobile.

[0007] The internal structure printing layer becomes visible or invisible due to a temperature change by the reversible thermochromic layer containing the reversible thermochromic composition. The reversible thermochromic composition comprises (A) an electron-donating color-forming organic compound, (B) an electron-accepting compound, and (C) a composition containing three components of a reaction medium that determines a temperature at which a color reaction of both occurs. Are preferably used, for example,
JP-B-51-44706, proposed by the present applicant,
JP-B-51-44707, JP-B-1-29398
Publications described in Japanese Patent Laid-Open Publication No. HEI 7-203 can be used. The composition discolors before and after a predetermined temperature (discoloration point) as a boundary, exhibits a decolored state in a temperature range higher than the color change point, and a color developed state in a temperature range lower than the color change point. Only one particular state can exist in a region. That is, the other state is maintained while the heat or cold required for the state to appear is applied, but returns to the state exhibited in the normal temperature range when the application of the heat or cold disappears, the hysteresis width. Is a heat decoloring type reversible thermochromic composition showing a relatively small thermochromic behavior. In addition, Japanese Patent Publication No. 4-1715 proposed by the present applicant.
4, JP-A-7-179777, JP-A-7-179
No. 33997, Japanese Unexamined Patent Publication No. 8-39936, etc. exhibit a large hysteresis characteristic, that is, the shape of a curve plotting a change in coloring density due to a temperature change is
The color changes in a temperature range below the low-temperature side discoloration point, following a significantly different path when the temperature is raised from the low-temperature side above the color-change temperature range and conversely, when the temperature is lowered from the high-temperature side above the color-change temperature. Heat-discoloring type thermochromic discoloration that can be alternately stored even after the state or the decoloring state in the temperature range above the high-temperature side discoloration point is removed after the application of the cold or heat required for the discoloration. Sexual color memory compositions can also be utilized.

Further, Japanese Patent Application Laid-Open No. H11-1 proposed by the present applicant
No. 29623, JP-A-11-5973, etc., specific alkoxyphenol compounds having a straight-chain or side-chain alkyl group having 3 to 18 carbon atoms as the (b) electron-accepting compound contained in the composition A heat-colorable reversible thermochromic composition to which is applied is also applicable. Further, as the electron accepting compound contained in the heat coloring type reversible thermochromic composition, 3-hydroxybenzoic acid tridecyl ester, 3-hydroxybenzoic acid tetradecyl ester, 3-hydroxybenzoic acid pentadecyl ester, 3 -Hexadecyl hydroxybenzoate, 3
-Heptadecyl hydroxybenzoate, octadecyl 3-hydroxybenzoate, nonadecyl 3-hydroxybenzoate, eicosyl 3-hydroxybenzoate, henicosyl 3-hydroxybenzoate, doco 3-hydroxybenzoate Sil ester, 4-hydroxybenzoic acid tridecyl ester, 4
-Tetradecyl hydroxybenzoate, pentadecyl 4-hydroxybenzoate, hexadecyl 4-hydroxybenzoate, heptadecyl 4-hydroxybenzoate, octadecyl 4-hydroxybenzoate, nonadecyl 4-hydroxybenzoate Esters, eicosyl 4-hydroxybenzoate, heneicosyl 4-hydroxybenzoate,
Docosyl 4-hydroxybenzoate, tridecyl 3,4-dihydroxybenzoate, tetradecyl 3,4-dihydroxybenzoate, pentadecyl 3,4-dihydroxybenzoate, hexa-3,4-dihydroxybenzoate Decyl ester, heptadecyl 3,4-dihydroxybenzoate, octadecyl 3,4-dihydroxybenzoate, nonadecyl 3,4-dihydroxybenzoate, eicosyl 3,4-dihydroxybenzoate, 3,4- Heneicosyl dihydroxybenzoate, docosyl 3,4-dihydroxybenzoate, tridecyl 3,5-dihydroxybenzoate, tetradecyl 3,5-dihydroxybenzoate, pentade 3,5-dihydroxybenzoate Ester, 3,5-dihydroxybenzoic acid hexadecyl ester, 3,5-dihydroxybenzoic acid heptadecyl ester, 3,5-dihydroxybenzoic acid octadecyl ester, 3,5-dihydroxybenzoic acid nonadecyl ester, 3,5-dihydroxy Hydroxybenzoic acid esters such as eicosyl benzoate, heneicosyl 3,5-dihydroxybenzoate and docosyl 3,5-dihydroxybenzoate can also be used.

The reversible thermochromic composition comprises (a)
The components (b) and (c) are essential components, and the ratio of each component is
Although it depends on the density, discoloration temperature, discoloration form, and the type of each component, generally, the component ratio at which desired characteristics can be obtained is as follows: component (a), component (b) component 0.1 to 50; Preferably 0.5 to 20, (c) component 1 to 200, preferably 5 to
100, more preferably in the range of 20 to 50 (all the above parts are parts by weight). In addition, each of the above (a),
The components (b) and (c) may each be a mixture of two or more compounds.

The reversible thermochromic composition is preferably used as a pigment in the form of microcapsules encapsulated in microcapsules. This is because it satisfies practicability such as sharp and high-concentration color development, homogeneity, dispersion stability, chemical resistance, heat resistance and the like. The microcapsules satisfy the practicality when they have a particle size of 0.1 to 100 μm, preferably 1 to 50 μm, more preferably 2 to 30 μm. The microencapsulation is performed by a conventionally known interfacial polymerization method, in
It can be prepared by a method such as a Situ polymerization method, a liquid curing coating method, a phase separation method from an aqueous solution, a phase separation method from an organic solvent, a melting dispersion cooling method, an air suspension coating method, and a spray drying method. Further, a secondary resin film may be further provided on the surface of the microcapsule pigment according to the purpose to impart durability, or the surface characteristics may be modified for practical use.

The reversible thermochromic composition or the microcapsule pigment containing the same is dispersed in a vehicle containing a resin and used as an ink or a paint, and is used in a conventionally known method such as tampo printing and transfer. The reversible thermochromic layer can be provided by printing means, brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, dip coating, or the like. The reversible thermochromic layer is a layer formed by other compounds after the solvent is volatilized, and the reversible thermochromic composition or the microcapsule pigment is fixed to a resin in a dispersed state. In the vehicle, ultraviolet absorbers, infrared absorbers, antioxidants, singlet oxygen quenchers, antioxidants, antistatic agents, thixotropic agents, defoamers,
Extenders, viscosity modifiers, dispersants, matting agents, penetrants,
Various additives such as a pH adjuster, a preservative, and a rust preventive can also be appropriately added.

Further, a reversible thermochromic composition is prepared by dispersing the reversible thermochromic composition in fine particles in a vinyl chloride-vinyl acetate copolymer resin as described in JP-A-6-135144. A discoloration layer can also be formed.

The reversible thermochromic three-dimensional object obtained as described above is further provided with a layer containing a light stabilizer and / or a light-shielding pigment to improve light resistance, or to provide a top coat layer. It can also be provided to improve durability. Examples of the light shielding pigment include pigments such as metallic luster pigment, transparent titanium dioxide, transparent iron oxide, transparent cesium oxide, and transparent zinc oxide.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The reversible thermochromic three-dimensional object of the present invention comprises:
After appropriately providing a printing layer drawn by a shading method showing an internal structure on a three-dimensional object, a reversible thermochromic layer is provided by applying or spraying a paint containing the reversible thermochromic composition on the printing layer. can get. When the three-dimensional object is formed of an opaque material, the reversible thermochromic layer is provided on the print layer as described above. When the three-dimensional object is formed of a transparent material, the reversible thermochromic layer is formed on the surface of the three-dimensional object. And a printing layer may be provided at a position (the back surface of the three-dimensional object) opposite to the reversible thermochromic layer.

[0015]

Examples are shown below. Parts in the examples are parts by weight.

Example 1 (see FIGS. 1 and 2) A shadow painting method showing a car engine by tampo printing using black ink and silver ink on the bonnet of a black miniature car made of ABS resin as the three-dimensional object 2 Was printed. On the internal structure printing layer 3, 3.0 parts of 3-dibutylamino-6-methyl-7-anilinofluoran, 6.0 parts of 2,2bis- (4-hydroxyphenyl) propane, and cetyl alcohol 2
20.0 parts of a microcapsule pigment (black at about 30 ° C. or less, colorless at 30 ° C. or more) containing a reversible thermochromic composition composed of 5.0 parts and 25.0 parts of stearyl caprate in an epoxy resin film. % Acrylic resin / xylene solution, 40.0 parts, xylene, 20.0 parts of methyl isobutyl ketone, 20.0 parts of methyl isobutyl ketone are uniformly stirred to obtain a reversible thermochromic ink, and the reversible thermochromic layer 4 is provided. A reversible thermochromic three-dimensional object 1 was obtained.

In the reversible thermochromic three-dimensional object 1, a black miniature car is visually recognized under an environment of 30 ° C. or less (FIG. 1), but when the bonnet part is touched, the reversible thermochromic layer is decolorized. Thus, the internal structure printing layer 3 is visually recognized, giving an appearance as if the engine housed inside was visually recognized (FIG. 2). This change could be made repeatedly by changing the temperature.

Example 2 A three-dimensional object was printed on the surface of a robot made of ABS resin by using a black ink and a silver ink by tampo printing to print an internal structure printing layer drawn by a shading method showing the internal structure of the robot. 3.0 parts of 3-cyclohexylamino-7-methylfluoran, 2,2
-Bis- (4-hydroxyphenyl) propane 6.0
Part, cetyl alcohol 25.0 parts, stearyl caprate 25.0 parts of a reversible thermochromic composition encapsulated in an epoxy resin film, a microcapsule pigment (shows an orange color at about 30 ° C. or less and becomes colorless at 30 ° C. or more. 20.0 parts)
A reversible thermochromic ink obtained by uniformly stirring 40.0 parts of a 50% acrylic resin / xylene solution, 20.0 parts of xylene, and 20.0 parts of methyl isobutyl ketone was spray-coated to form a reversible thermochromic layer. A reversible thermochromic solid was obtained.

In the reversible thermochromic three-dimensional object, an orange robot can be visually recognized in an environment of 30 ° C. or lower. However, when the robot is immersed in warm water of 30 ° C. or higher, the reversible thermochromic layer is decolorized and the internal structure is reduced. The printed layer is visually recognized, giving an appearance as if the internal machine was visually recognized. This change could be made repeatedly by changing the temperature.

Example 3 A three-dimensional printed material having an internal structure printed layer drawn on a bonnet of a black miniature car made of ABS resin by a shadow printing method using a black ink and a silver ink by tampo printing using a car engine. Printed. 3.0 parts of 3-dibutylamino-6-methyl-7-anilinofluoran, 6.0 parts of 2,2 bis- (4-hydroxyphenyl) propane, and cetyl alcohol 25.
0 parts, 20.0 parts of a reversible thermochromic composition comprising 25.0 parts of stearyl caprate in an epoxy resin film (black at about 30 ° C. or less, colorless at 30 ° C. or more), 50% acrylic Resin / xylene solution 4
A reversible thermochromic ink obtained by uniformly stirring 0.0 parts, 20.0 parts of xylene and 20.0 parts of methyl isobutyl ketone was spray-coated to form a reversible thermochromic layer. Then, on the reversible thermochromic layer, a metal luster pigment (trade name RCFSX-5090RC (8069), manufactured by Nippon Glass Fiber Co., Ltd., trade name: RCFSX-5090RC (8069), average thickness 5 ± 2 μm) Average particle size 90 ± 30 μm] 15 parts, 50
% Acrylic resin / xylene solution 45.0 parts, xylene 2
A metallic glossy ink obtained by uniformly stirring 0.0 parts and 20.0 parts of methyl isobutyl ketone was spray-coated to provide a metallic glossy layer to obtain a reversible thermochromic solid.

In the reversible thermochromic three-dimensional object, under an environment of 30 ° C. or less, a metallic blue miniature car is visually recognized, but when the bonnet part is touched, the reversible thermochromic layer is discolored and the internal structure is reduced. The printed layer is visually recognized, giving an appearance as if the engine housed inside was visually recognized.
This change could be made repeatedly by changing the temperature.

[0022]

According to the present invention, the internal structure printed on the surface of the three-dimensional object drawn by the shading method is concealed by the reversible thermochromic layer. It is possible to provide a reversible thermochromic three-dimensional object which can give an appearance in an invisible state and is simple and excellent in commercial properties.

[Brief description of the drawings]

FIG. 1 is a perspective view showing a state in which a reversible thermochromic layer of one embodiment of the present invention has developed color.

FIG. 2 is a perspective view showing a state in which a reversible thermochromic layer of the reversible thermochromic three-dimensional object in FIG. 1 is decolorized.

[Explanation of symbols]

 Reference Signs List 1 reversible thermochromic three-dimensional object 2 three-dimensional object 3 internal structure printing layer 4 reversible thermochromic layer

Claims (1)

[Claims] 1. An inner structure printing layer drawn on a surface of a three-dimensional object by a shading method showing an inner structure of the three-dimensional object, and a reversible thermochromic layer for reversibly concealing the inner structure printing layer by a temperature change. And a reversible thermochromic three-dimensional object.