JP3172809B2 - Thermochromic laminate and composition and sheet used to produce this laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a silvery metallic luster thermochromic laminate and to coating compositions and sheets used to form the laminate. More specifically, the present invention relates to a thermochromic laminate having a metallic luster exhibiting a color change from silver due to a temperature change, and a coating composition and a sheet used for forming the laminate.

[0002]

2. Description of the Related Art Conventionally, thermochromic materials exhibiting a reversible color change of colored ← → colorless and colored [1] ← → colored [2] due to temperature change are disclosed in Japanese Patent Publication No. 51-44706 and Japanese Patent Publication No. Sho 5-5.
JP-A-1-44707, JP-B-51-44708, JP-B-52-7776, and JP-B-51-465.
No. 48, JP-A-62-140881, and the like, and a thermochromic material colored using the thermochromic material is practically used as a temperature indicating element, a toy element, a magic element, or the like.

However, a thermochromic material exhibiting a reversible change from a silver metallic luster color to colorless due to a temperature change, and a reversible color change to another different color, and a thermochromic material capable of clearly expressing the color change Is not yet known. In addition, attempts to diversify the color change have been made in Japanese Utility Model 3-14400.
No. 6,086,045. The thermochromic material described in this publication is intended to cover the thermosensitive liquid crystal with a pearl luster layer so as to develop a pearlescent color change.

However, liquid crystals are inherently colorless and reflect a specific wavelength, which is the selective scattering of visible light. Therefore, a blackish opaque layer is required on the back surface.
Since the color looks black-red-yellow-green-blue-purple-black, the color change does not become clear even if a pearlescent layer is provided thereon.
For example, when a silver pearlescent pigment is used, the color change is silver-silverish red-silverish yellow-silverish green-silverish blue-silverish purple-silverish, giving a metallic luster. No clear change to no color.
In addition, a color change from pearl luster color to colorless color cannot be developed, and the base cannot be concealed or revealed.
Since silver is a gorgeous and conspicuous color and the change from silver attracts the attention of the viewer, there has been a great demand for a material that makes such a color change.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have conducted research to make the discoloration effect of the thermochromic material effective and to make the color change from silver metallic luster to vivid and colorful thermal discoloration. It was. Thermochromic material used in the present invention, unlike liquid crystal, because there is a clear color change in the thermochromic material itself, there is no need to provide a dark opaque layer in the lower layer,
In addition, there is a feature that the color-colorless change is possible. It looks white when all visible light is reflected. In this case, when a part of the light of all the wavelengths of the incident light is absorbed and the rest is reflected, the light becomes dark and gray. Since the mica is arranged in layers, the reflected light is reflected in the same direction without irregular reflection. Such reflected light has metallic luster. Therefore, gray with metallic luster becomes silver. Thus, a silver surface with a metallic luster is exposed. Also, a clear color change from a silver metallic glossy color to a colored color by mixing a non-discoloring colorant can be made visible to a viewer. Further, a configuration in which the lower colored layer is concealed with a metallic luster color can be adopted. This kind of color change or hiding cannot be exhibited in the liquid crystal system. Furthermore, by using a thermochromic material having a very large hysteresis width as a thermochromic material, a so-called color material containing a so-called color memory thermosensitive dye, the state changed even after removing the heat or cold required for thermochromic discoloration. It can be maintained and also has the effect that the state can be visually recognized in a normal temperature range. Since the color change due to the heat of the silver metallic luster color is clearly expressed in this way, the present invention is widely used in the decorative field, the intellectual field, toys, stationery, and information fields.

[0006]

Means for Solving the Problems The present invention provides: "1. A. The optical thickness of a coating layer in which the surface of natural mica is coated with 16 to 39% by weight of titanium oxide is 110 to 170%.
B. a layer for adjusting the wavelength of reflected light, comprising a silver metallic luster pigment having a particle size of 5 to 100 μm and a film-forming material, as a first layer; A thermochromic material composed of an electron-donating compound, an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between the two. A thermochromic laminate that reversibly changes from silver metallic luster color to colorless, wherein a layer formed of a thermochromic material having a value of 8 or more and a film-forming material is a second layer. 2. A. The first layer is (a) the surface of natural mica 16-39
The optical thickness of the coating layer coated with 1% by weight of titanium oxide is 1
A silver metallic luster color coating layer formed by coating a coating composition comprising a silver metallic luster pigment having a particle size of 10 to 170 nm and a particle size of 5 to 100 μm, a coating film forming material, and a coloring agent; A) a silver metal molded from a silver metallic luster pigment having a particle size of 5 to 100 μm and a synthetic resin having an optical thickness of 110 to 170 nm and a particle size of 5 to 100 μm; B. a layer for adjusting the wavelength of reflected light selected from a gloss coloring sheet; The second layer is (a) a thermochromic material comprising an electron-donating compound, an electron-accepting compound, and an organic compound medium which reversibly causes a color reaction between the two and has a lightness value of color density of 6 or less in a colored state. A layer formed by coating a colorless thermochromic material in a decolored state having a lightness value of 8 or more, a coating composition comprising a coating film forming material and a vehicle, and (b) an electron donating compound and electron accepting property A thermochromic material comprising a compound and an organic compound medium capable of reversibly causing a color reaction between the compound and a thermochromic material having a color density lightness value of 6 or less and a colorless lightness value of a decolorized state of 8 or more. 2. The thermochromic laminate described in item 1, which is a thermochromic layer selected from a material and a thermochromic sheet molded from a synthetic resin, the thermochromic laminate reversibly changing color from silver metallic luster to colorless. 3. The second thermochromic layer is a thermochromic material in which a non-thermochromic colored dye or pigment is blended, and the lightness value (V1) of the color density of the mixed system at the time of color development is 6 or less, and the mixing at the time of decolorization. If the lightness value (V2) of the colored system is 4 or more and (V2)-(V
1) The thermochromic laminate which reversibly changes color from a silver metallic luster color to a color of a dye or pigment as described in 1 or 2, wherein> 1. 4. 4. The thermochromic layer of the thermochromic laminate which reversibly changes from a silver metallic luster color to a colorless or dye pigment color according to any one of the items 1 to 3, followed by a non-thermochromic layer The lightness value (V3) of the color density formed by the colored dye or pigment and the film forming material is 4 or more, and is between (V3)-(V4) between the lightness value (V4) of the thermochromic material at the time of color development. A thermochromic laminate in which a non-thermochromic dye / pigment coloring layer that satisfies the relationship of> 1 is arranged and reversibly changes color from a silver metallic luster color to a dye / pigment color. 5. 5. The thermochromic material according to any one of items 1 to 4, wherein the thermochromic material is a thermochromic material obtained by encapsulating a microcapsule with an organic compound medium that reversibly causes a color reaction between the electron-donating compound and the electron-accepting compound. The described thermochromic laminate which reversibly changes from a silver metallic luster color to a colorless or dye pigment color. 6. 6. A thermochromic granule obtained by cutting and powdering the thermochromic laminate according to any one of items 1 to 5, which reversibly changes from a silver metallic luster color to a colorless or dye pigment color. 7. 6. A thermochromic yarn formed by cutting a thermochromic laminate which reversibly changes from a silver metallic luster color to a colorless or dye pigment color according to any one of items 1 to 5, and formed into a thread shape. 8. A. The optical thickness of the coating layer in which the surface of natural mica is coated with 16 to 39% by weight of titanium oxide is 110 to 170 n.
B. a coating composition comprising a silver metallic luster pigment having a particle size of 5 to 100 μm, a coating film forming material, and a vehicle; A lightness value of a color density of 6 or less and a colorless lightness value of a decolored state of 8 or more composed of an electron-donating compound, an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between the two. A thermochromic laminate that reversibly changes color from a silver metallic luster color to colorless by combining two types of coating compositions consisting of a thermochromic material, a film forming material, and a coloring agent. Two-pack type combination coating material for body formation. 9. When a coating composition comprising a thermochromic material, a film-forming material, and a coloring agent is blended with a non-thermochromic colored dye or pigment, the lightness value (V1) of the color density of the mixed system is 6 or less. 7. The reversibly silvery metallic luster described in item 8, which is a thermochromic composition having a color value (V2) of 4 or more and (V2)-(V1)> 1 when the color is decolorized. A two-pack combination coating material for forming thermochromic laminates that changes color from dye to pigment. 10. A. The optical thickness of the coating layer obtained by coating the surface of natural mica with 16 to 39% by weight of titanium oxide is 110 to 170.
B. a coating composition comprising a silver metallic luster pigment having a particle size of 5 to 100 μm, a coating film forming material and a vehicle; (A) A colorless lightness value of a colorless state in a colorless state of 6 or less and a colorless lightness value of an electron-donating compound, an electron-accepting compound, and an organic compound medium capable of reversibly causing a color reaction between them. A coating composition comprising a thermochromic material, a coating film forming material, and a coloring agent having a molecular weight of 8 or more; and (b) an organic compound that reversibly causes a color reaction between the electron-donating compound and the electron-accepting compound. A non-thermochromic colored dye for a thermochromic material, a film-forming material, and a colorant having a color density lightness value of 6 or less and a colorless lightness value of a decolored state of 8 or more composed of a compound medium. Alternatively, the lightness value (V1) of the color density of the mixed system at the time of color formation containing the pigment is 6 or less, and the lightness value (V2) of the mixed system at the time of decoloring is 4 or more (V2).
C. a coating composition of (V1)> 1 and a thermochromic composition selected from the group consisting of: The lightness value (V3) of the color density formed by the non-thermochromic dye or pigment, the coating film forming material, and the colorant is 4 or more and between the lightness value (V4) of the thermochromic material at the time of color development. To (V
3) A non-thermochromic dye / pigment colored coating composition that satisfies the relationship of-(V4)>1; Three-component combination coating for forming thermochromic laminates that change color
Wood . 11. Item 8. The thermochromic material according to item 8 to 10, wherein the thermochromic material is a thermochromic material obtained by encapsulating a microcapsule with an electron-donating compound and an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between both. The combination coating material for forming a thermochromic laminate, which reversibly changes from a silver metallic luster color to a colorless or dye / pigment color as described in any one of the above items. 12. A. The optical thickness of the coating layer obtained by coating the surface of natural mica with 16 to 39% by weight of titanium oxide is 110 to 170.
B. a silver metallic gloss coloring sheet formed of a silver metallic gloss pigment having a particle size of 5 to 100 μm and a resin; A lightness value of a color density of 6 or less and a colorless lightness value of a decolored state of 8 or more composed of an electron-donating compound, an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between the two. A sheet for forming a thermochromic laminate that reversibly changes color from a silver metallic luster color to colorless, which is a combination of two kinds of sheets: a thermochromic material formed of a thermochromic material and a resin. 13. When the thermochromic sheet contains a non-thermochromic colored dye or pigment in addition to the thermochromic material, the lightness value (V1) of the color density of the mixed system at the time of color development is 6 or less, and the color of the mixed system at the time of decoloring is 6 or less. The brightness value (V2) is 4 or more and (V2)-(V1)>
Item 1. The sheet for forming a thermochromic laminate according to Item 12, which is a thermochromic sheet, which reversibly changes from a silver metallic luster color to a dye pigment color. 14． A. The optical thickness of the coating layer obtained by coating the surface of natural mica with 16 to 39% by weight of titanium oxide is 110 to 170.
B. a silver metallic gloss coloring sheet formed of a silver metallic gloss pigment having a particle size of 5 to 100 μm and a resin; (A) A colorless lightness value of a colorless state in a colorless state of 6 or less and a colorless lightness value of an electron-donating compound, an electron-accepting compound, and an organic compound medium capable of reversibly causing a color reaction between them. A sheet formed of a thermochromic material having a color difference of 8 or more; and (b) a color-developed state comprising a synthetic resin and an electron-donating compound and an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between the two. The color density of a mixed system at the time of color development in which a non-thermochromic colored dye or pigment is blended in addition to a thermochromic material having a colorless lightness value of 6 or less and a decolorized colorless lightness value of 8 or more The lightness value (V1) of the mixed system at the time of decoloring is 6 or less and the lightness value (V2) of the mixed system is 4 or more and (V2) −
(V1)> 1 sheet, and a thermochromic sheet selected from: The non-thermochromic colored dye or pigment is mixed with the synthetic resin, and the lightness value (V3) of the color density is 4 or more, and the lightness value (V3) of the thermochromic material at the time of color development is (V3)- (V
4) A three-way combination sheet for forming a thermochromic laminate that reversibly changes from a silver metallic glossy color to a dye / pigment color, which is a combination of three types of sheets, a colorable sheet, which satisfies the relationship of> 1. 15. Item 12. The thermochromic material according to item 12 to 14, wherein the thermochromic material is a thermochromic material obtained by encapsulating an organic compound medium which reversibly causes a color reaction between the electron-donating compound and the electron-accepting compound and both. The combination sheet for forming a thermochromic laminate, which reversibly changes color from silver to colorless or color of a dye or pigment as described in any one of the above items. About.

The silver metallic luster pigment used in the present invention is:
Specifically, it is a silver-colored pigment in which the surface of natural mica particles is coated with titanium oxide. More specifically, the silver metallic luster pigment has the surface of natural mica particles coated with 16 to 39% by weight of titanium oxide.
Optical thickness of coating layer 110-170 nm, particle size 5-10
It is 0 μm.

[0008] The optical thickness of the coating layer of the present invention is the refractive index ×
Geometric thickness, which is associated with reflecting certain wavelengths. In other words, a specific optical thickness reflects light of a specific wavelength,
The titanium oxide layer of 110 to 170 nm formed on the surface of natural mica reflects silver light of 380 to 700 nm. As the thermochromic layer, a thermochromic material containing three components of an organic compound medium that reversibly causes a color reaction between the electron donating color compound and the electron accepting compound is used.

Most preferably, the thermochromic material is used by being encapsulated in microcapsules. This is because the thermochromic materials are maintained at the same composition under various use conditions and can exhibit the same effects.

The thermochromic laminate of the present invention comprises a layer in which the silver metallic luster pigment and the thermochromic material are bonded by a transparent film-forming material. The lightness value in the present invention is a lightness value of a Munsell color chart system in which a perfect black is set to 0 and a perfect white is set to 10 in an achromatic array, and the interval between them is divided so that the difference in sense of brightness is equally spaced. , And the chromatic lightness indicates an achromatic lightness value whose sensation of the chromatic color brightness is equal to this.
In other words, the smaller the brightness value, the closer to black, and the larger the brightness value, the closer to white, it can be used as an index of how much visible light is absorbed and how much it is reflected. It indicates how visible light transmitted through the gloss pigment layer is reflected and absorbed by the thermochromic layer thereunder.

[0011]

The heat-modified laminate of the present invention is a laminate in which a silver metallic luster pigment layer is laminated on a thermochromic layer, and the color change of the thermochromic layer is passed through the silver metallic luster pigment layer. It is something that makes you visually. As described above, when all visible light is reflected, it appears white. In this case, when a part of the light of all the wavelengths of the incident light is absorbed and the rest is reflected, the light becomes dark and gray.

Since the mica is arranged in layers, the reflected light is reflected in the same direction without irregular reflection. Such reflected light has metallic luster. Therefore, gray with metallic luster becomes silver. Thus, a silver surface with a metallic luster is exposed. What is important here is that the titanium oxide has an optical thickness of 110.
１７０170 nm. If the optical thickness is out of the above range, wavelength selectivity of the reflected light occurs and the color is not turned to silver.

When a layer containing a non-color-changing dye / pigment coloring agent is used as the thermochromic layer, a reversible color change from a silver metallic glossy color to a colored colorant is observed. Since the silver metallic luster pigment layer is transparent, if a non-discoloring colored layer is disposed as the lowermost layer, the color of this colored layer can be visually recognized simultaneously with the thermal discoloration of the thermochromic layer. In the colored state of the thermochromic layer, the lower non-color-changing colored layer, for example, characters, patterns, etc. are also concealed. At this time, the concealing effect is smaller than the concealing effect of only thermochromic due to the light reflection effect of the silver metallic luster pigment layer. Enhance. As described above, the thermochromic layer uses three components of an organic compound medium that reversibly causes a color reaction between the electron donating color compound and the electron accepting compound.

More specifically, for example, the aforementioned Japanese Patent Publication No. 51-35
No. 414, etc. (1) The essential components include (a) an electron-donating color-forming organic compound, (b) a compound having a phenolic hydroxyl group, and (c) a linear aliphatic monohydric alcohol having no polar substituent. Reversible thermochromic material. Or (2) (a) a compound having an electron-donating color-forming organic compound, (b) a compound having a phenolic hydroxyl group, (c) an aliphatic monohydric alcohol having no polar substituent, and having a polar substituent. A reversible thermochromic material comprising, as essential components, three components of a compound selected from an ester having no polar substituent obtained from an aliphatic monocarboxylic acid which is not obtained. Or (3) (a) an electron-donating color-forming organic compound, (b) a compound having a phenolic hydroxyl group, and (c) a higher alicyclic monohydric alcohol having no polar substituent, and a polar substitution. It is composed of three components, a compound selected from an aliphatic monocarboxylic acid having no group and an ester having no polar substituent obtained from a linear aliphatic monohydric alcohol having no polar substituent. Reversible thermochromic material. Or (4) (a) an electron-donating color-forming organic compound, (b) a compound having a phenolic hydroxyl group, (c) a higher aliphatic monohydric alcohol having no polar substituent, and a polar substituent. The essential component is a compound selected from a polar non-substituted ester obtained from a higher aliphatic monocarboxylic acid having no polar group and a linear aliphatic monohydric alcohol having no polar substituent. Thermochromic material. And so on.

[0015] In addition, a thermochromic material containing a color-memorizing thermochromic dye which exhibits a large hysteresis characteristic and discolors as described in JP-A-60-264285, that is, a change in coloring density due to a temperature change The shape of the curve in which the color is plotted changes color following a route that is significantly different depending on whether the temperature rises from a temperature lower than the discoloration temperature range or vice versa. A thermochromic material having a characteristic of being able to memorize and retain a state changed at a temperature equal to or lower than the low-temperature color changing point or equal to or higher than the high-temperature color changing point in a normal temperature range between the low-temperature color changing points. The thermochromic debris of the present invention will be specifically described.

The thermochromic laminate of the present invention has the following (A)
(C) the laminate. (A) A laminate in which a silver metallic luster pigment layer is laminated on a thermochromic layer. (B) A laminate in which a thermochromic material is mixed with a non-chromogenic dye / pigment, and a silver metallic luster pigment layer is laminated on the thermochromic layer. (C) A laminate in which a thermochromic layer is laminated on a non-chromogenic coloring layer, and a silver metallic luster pigment layer is laminated on the thermochromic layer. The thermochromic laminate may be directly laminated on the support, or a clear coat layer or a transparent laminate layer may be interposed between the thermochromic layer and the silver metallic luster pigment layer,
A transparent protective film may be laminated on the silver metallic luster pigment layer. Alternatively, a laminate may be formed without using a support.

In the laminate (A), the silver metallic luster pigment layer is a layer in which a silver metallic luster pigment having a particle size of about 5 to 100 μm is fixed in a transparent resin in a dispersed state,
The thermochromic material is a thermochromic material (hereinafter, referred to as a thermochromic material) comprising a three-component homogeneous solution of an electron-donating color-forming organic compound, an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between the two. The thermochromic material is a thermochromic material having the above-mentioned structure) and is fixed in a dispersed state with a transparent film-forming material. A colorless colorless layer having a colorless lightness value of 8 or more, comprising a silvery metallic glossy thermochromic laminate exhibiting a reversible color change from a silvery metallic glossy colorless to a colorless to a silvery metallic glossy color. Is done. When the lightness value of the color density in the color-developed state is 6 or less, there is an ability to sufficiently absorb light transmitted through the silver metallic luster pigment in the upper layer. For example, in the case of a silver metallic luster pigment, the silver metallic luster pigment is clearly Looks glossy. But,
If the lightness value of the colored state exceeds 6, the light transmitted through the silver metallic luster pigment cannot be sufficiently absorbed, and some of the light is reflected again, so that the colored metallic luster color cannot be seen clearly. On the other hand, if the colorless lightness value of the decolored state is 8 or more, it has the ability to sufficiently reflect light transmitted through the silver metallic luster pigment, and thus reflects light reflected by the silver metallic luster pigment and thermochromic material. The mixed light returns to white light,
Does not look silver.

In the laminate of (B), the silver metallic luster pigment layer is a layer in which a silver metallic luster pigment of about 5 to 100 μm is fixed in a dispersed state in a transparent resin, and the thermochromic layer is the thermochromic layer. A lightness value (V ₁ ) of a color density in a color-developed state in which a color-changing material and a non-color-changing colorant (dye, pigment) are mixed.
Is 6 or less, and the color value (V ₂ ) of the decolored state is 4 or more, and the brightness value (V ₂ ) −the brightness value (V ₁ )> 1 is satisfied. Thus, a silver metallic luster thermochromic laminate showing a reversible color change from metallic luster to colored, and colored to silver metallic luster is formed. The reason why the lightness value (V ₁ ) of the color density of the color mixture in the color development state is 6 or less is the same as described above. On the other hand, the reason why the color value (V ₂ ) of the mixed color system in the decolored state needs to be 4 or more and the above-mentioned V ₂ −V ₁ > 1 must be satisfied is that the non-color-change colorant, the non-thermal Since the discolorable dyes and pigments are mixed and become colored, the lightness value becomes small and fluctuates depending on the color of the dye or pigment. For example, the brightness value is relatively large for yellow, orange, and the like, and is small for red, purple, and the like. However, in order to obtain a satisfactory color change, the lightness value in the decolored state needs to be at least greater than 1 in the color development state. Not clear. If there is a lightness value of 4 or more under such conditions, for example, a reversible color change from silver to color and from color to silver can be exhibited. However, if it is less than 4, the color density of the underlying color mixture layer becomes too dark, and the silver color is seen even in the decolored state.

In the laminate of (C), the lightness value (V ₃ ) of the color density below the thermochromic layer is 4 or more, and the lightness value (V4) of the color development state of the thermochromic layer is between V3-V4>
A non-color-changing colored layer that satisfies the relationship of No. 1 is formed, and a silver metallic glossy thermochromic laminate exhibiting a reversible color change between the silver metallic gloss color and the color of the non-color-changing colored layer is formed. You.
Note that, as described above, the lower the lightness value of the thermochromic material at the time of decoloring, the closer to black, and the higher the lightness value, the closer to white light, so how much visible light is absorbed and how much is reflected This index indicates how the visible light transmitted through the silver metallic luster pigment layer is reflected and absorbed by the thermochromic layer thereunder. Therefore, if the thermochromic layer has a lightness value of 6 or less, the thermochromic layer has an ability to sufficiently absorb visible light transmitted through the silver metallic luster pigment, and as a result, only silver light reflected by the silver metallic luster pigment layer is visible. Because you can
Looks silver. Conversely, when the brightness value becomes 8 or more,
Since it reflects visible light that has passed through the silver metallic luster pigment layer, both the light reflected by the silver metallic luster pigment layer and the light reflected by the thermochromic layer will be seen together. Disappears.

That is, it is an index of whether the thermochromic material has a characteristic of appearing silver below the discoloration temperature and disappearing above the discoloration temperature. The brightness value of the present invention was determined by using a sample adjusted as described below for a TC-360 manufactured by Tokyo Denshoku Co., Ltd.
It is a value obtained by measurement using a 0 color difference meter. 1. Measurement of lightness value of thermochromic layer (including a system in which non-color-changing dye / pigment is mixed) (1) Measurement of lightness value of thermochromic layer (color ← → colorless) Thermochromic material 10 parts, 50% acrylic acid Ester resin /
45 parts of a xylene solution, 20 parts of xylene and 20 parts of methyl isobutyl ketone were stirred and mixed, spray-coated on a white vinyl chloride sheet having a lightness value of 9.1 with a spray gun, and dried to form a thermochromic layer having a thickness of 40 μm. Prepare. The lightness value of the color-developed state and the decolored state of the obtained thermochromic layer is measured. (2) Measurement of lightness value of thermochromic layer (color I ← → color II) 10 parts of thermochromic material, desired amount of non-thermochromic dye / pigment, 50 parts
% Acrylate resin / 45 parts of xylene solution, 20 parts of xylene and 20 parts of methyl isobutyl ketone were stirred,
The mixture was mixed, spray-coated on a white vinyl chloride sheet having a lightness value of 9.1 with a spray gun, and dried to a thickness of 40 μm.
Is prepared. The lightness value of the color-developed state and the decolored state of the obtained thermochromic layer is measured. 2. Non-color-change coloring layer (coloring with non-thermo-color dye)
Measurement of lightness value A desired amount of a non-thermochromic dye / pigment, 45 parts of a 50% acrylate resin / xylene solution, 20 parts of xylene and 20 parts of methyl isobutyl ketone were stirred and mixed to obtain a lightness value of 9.1.
Is spray-coated on a white vinyl chloride sheet with a spray gun to prepare a 10 μm-thick non-discoloring colored layer after drying. The lightness value of the obtained non-discoloring colored layer is measured.

Next, a film forming material will be exemplified. Ionomer resin, isobutylene-maleic anhydride resin copolymer resin,
Acrylonitrile-acrylic styrene copolymer resin,
Acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile-chlorinated polyethylene-styrene copolymer resin, ethylene-vinyl chloride copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate-vinyl chloride Graft copolymer resin, vinylidene chloride resin, vinyl chloride resin, chlorinated vinyl chloride resin, vinyl chloride-vinylidene chloride copolymer resin, chlorinated polyethylene resin, chlorinated polypropylene resin, polyamide resin, high-density polyethylene resin, medium-low density polyethylene Resin, linear low density polyethylene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin, polystyrene resin, high impact polystyrene resin, polypropylene resin, polymer Rusuchiren resins, polyacrylate resins, polymethyl methacrylate resins, epoxy acrylate resins. Alkyl phenol resin, rosin modified phenol resin, rosin modified alkyd resin, phenol resin modified alkyd resin, epoxy resin modified alkyd resin, styrene modified alkyd resin, acryl modified alkyd resin, amino alkyd resin, vinyl chloride-vinyl acetate resin, styrene-butadiene resin , Epoxy resin, unsaturated polyester resin, polyurethane resin, vinyl acetate emulsion resin, styrene-butadiene emulsion resin, acrylate emulsion resin, water-soluble alkyd resin, water-soluble melamine resin, water-soluble urea resin,
Water-soluble phenol resin, water-soluble epoxy resin, water-soluble polybutadiene resin. Cellulose derivatives such as cellulose acetate and ethyl cellulose are exemplified. In the present invention, the above-mentioned resin is called a synthetic resin, and is appropriately selected from the above-mentioned resins according to the purpose and applied. Each layer of the thermochromic laminate of the present invention includes a coating film formed by applying a coating composition.

Next, the coating composition will be described. As the coating composition, the above-mentioned film-forming material alkylphenol resin, rosin-modified phenolic resin, rosin-modified alkyd resin, phenolic resin-modified alkyd resin, epoxy resin-modified alkyd resin, styrene-modified alkyd resin, acrylic-modified alkyd resin, aminoalkyd resin , Vinyl chloride-vinyl acetate resin, styrene-butadiene resin, epoxy resin, acrylate resin, unsaturated polyester resin, polyurethane resin, vinyl acetate emulsion resin, styrene-butadiene emulsion resin, acrylate emulsion resin, water-soluble Water-soluble alkyd resin, water-soluble melamine resin, water-soluble urea resin, water-soluble phenol resin, water-soluble epoxy resin, water-soluble polybutadiene resin, cellulose derivative, etc. Dissolved or dispersed composition is used.

In addition, each layer of the thermochromic laminate of the present invention comprises:
Molded sheets containing each pigment or thermochromic material are also included. These sheets include the ionomer resin, isobutylene-maleic anhydride resin copolymer resin, acrylonitrile-acrylic styrene copolymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile of the above-mentioned film-forming materials. -Chlorinated polyethylene-styrene copolymer resin,
Ethylene-vinyl chloride copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate-vinyl chloride graft copolymer resin, vinylidene chloride resin, vinyl chloride resin, chlorinated vinyl chloride resin, vinyl chloride-vinylidene chloride copolymer resin , Chlorinated polyethylene resin, chlorinated polypropylene resin, polyamide resin, high density polyethylene resin, medium and low density polyethylene resin, linear low density polyethylene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin, polystyrene resin, high impact polystyrene resin , Polypropylene resin, polymethylstyrene resin, polyacrylate resin, polymethylmethacrylate resin, epoxy resin, epoxyacrylate resin, alkyd resin, polyurethane resin , Resins etc. are used. The laminate of the present invention can use both a sheet and a coating film. It is preferable to use a transparent resin for the metallic luster pigment layer.
The laminate can be formed on the surface of the substrate, or can be formed as a laminated film without using the substrate. As the substrate, in addition to various films and sheets, the surface of the molded article itself is used. That is, a thermochromic molded article can be formed by forming a thermochromic debris on the surface of the molded article.
As the base material, paper, synthetic paper, cloth, nonwoven fabric, synthetic leather, leather, plastic, glass, ceramics, metal, wood, stone, and the like are used. In addition, not only a flat surface but also a surface having a processed surface such as an uneven surface or a fibrous surface can be used.

The laminate is formed by a conventionally known method, for example, printing means such as screen printing, offset printing, gravure printing, coater, tampo printing, transfer, brush coating, spray coating, electrostatic coating, electrodeposition coating. , Flow coating, roller coating, dip coating, and the like. It is also possible to form a film-sheet by extrusion or the like and to bond them together, or to obtain a thermochromic layer and a metallic luster pigment layer by multilayer molding. Incidentally, an ultraviolet absorber, an infrared absorber, an antioxidant, a singlet oxygen quencher, an antioxidant, an antistatic agent, a polarity imparting agent, a thixotropic agent, an antifoaming agent, a stabilizer,
Additives such as a plasticizer, a flame retardant, an extender, a lubricant, and a foaming agent can be added to the clear coat layer, the metallic luster pigment layer, and the thermochromic layer as needed.

[0025]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will now be described with reference to the drawings. Example 1 FIG. 1 shows Example 1 of the present invention, where 1 is a thermochromic laminate consisting of two layers. 3 is an optical thickness of 140 nm of a coating layer obtained by coating the surface of natural mica with 29% by weight of titanium oxide,
This is a first layer having a thickness of about 40 μm and made of a silver metallic luster pigment having an average particle size of 10 to 60 μm and an acrylate resin, and has a function of adjusting the wavelength of reflected light.
4 is incident light, and 5 is reflected light. Of the incident light 4, 6 that has not been reflected is absorbed by the thermochromic layer 2. The thermochromic layer 2 is made of a thermochromic composition comprising a compatibilizer of 3-anilino-3-methyl-6-dibutylaminofluoran (3 parts), bisphenol A (6 parts), and neopentyl stearate (50 parts). The thermochromic material A is a microcapsule having an average particle size of 8 μm obtained by microencapsulation according to the interfacial polymerization method, having a lightness value of 2.2 at the time of color development and 9.0 at the time of decolorization. This is a second layer having a thickness of about 40 μm and made of an acrylic acid ester resin, and reversibly develops and decolors by heat. At 15 ° C. or lower, the thermochromic layer develops a color, reflects light 5 which is a part of the visible light of incident light, and absorbs light 6 of other wavelengths to become a silver metallic glossy color and heat at 30 ° C. The color of the discoloration layer is erased, and the transmitted light 6
Is reflected, all the incident light is reflected, and the silver metallic luster disappears and becomes colorless. Parts in the above examples are parts by weight. The same applies to the parts in the following examples.

Example 2 2-anilino-3-methyl-6 was replaced with 2-anilino-3-methyl-6-dibutylaminofluoran of Example 1.
-1 part of dibutylaminofluoran, 1,3-dimethyl-
Same as Example 1 except that 2 parts of 6-diethylaminofluorane was used, and a thermochromic material prepared in the same manner and having a color value of 2.7 and a color value of 8.8 when decolorized was used. did. Similarly, at a temperature of 15 ° C. or less, a silver metallic luster color is obtained,
At 30 ° C. or higher, the silver metallic luster disappears and becomes colorless.

Example 3 In place of 2-anilino-3-methyl-6-dibutylaminofluorane of Example 1, 2-N, N-dibenzylamino-6-diethylaminofluorane was replaced by 2.5 parts. Example 1 was the same as Example 1 except that the prepared thermochromic material having a lightness value at the time of color development of 3.0 and a lightness value at the time of decoloration of 8.7 was used. Similarly, when the temperature is 15 ° C. or lower, the color becomes a silver metallic glossy color, and when the temperature is 30 ° C. or more, the silver metallic glossy color disappears and becomes colorless.

Example 4 3- (4-diethylamino-2) was used in place of 2-anilino-3-methyl-6-dibutylaminofluoran in Example 1.
-Ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide was 1.5 parts, and the lightness value at the time of color development was 3.2, and the lightness at the time of decolorization was similarly prepared. Example 1 was the same as Example 1 except that a thermochromic material having a value of 8.7 was used. Similarly, when the temperature is 15 ° C. or lower, the color becomes a silver metallic glossy color, and when the temperature is 30 ° C. or more, the silver metallic glossy color disappears and becomes colorless.

Example 5 In place of the silver metallic luster pigment of Example 1, the surface of natural mica was coated with 38% by weight of titanium oxide and had an optical thickness of 16%.
Example 1 was the same as Example 1 except that a silver metallic luster pigment having a particle size of 5 to 20 μm was used at 0 nm. Similarly, when the temperature is 15 ° C. or lower, the color becomes a silver metallic glossy color, and when the temperature is 30 ° C. or more, the silver metallic glossy color disappears and becomes colorless.

Example 6 In the laminate 1 shown in FIG. 2, the thermochromic layer 7 was formed from a compatible material of 3-part 2-anilino-3-methyl-6-dibutylaminofluorane, 6 parts bisphenol A, and 50 parts neopentyl stearate. A thermochromic material in the form of microcapsules having an average particle size of 8 μm obtained by microencapsulation of the thermochromic composition obtained by interfacial polymerization of an epoxy resin / amine-based curing agent, a fluorescent yellow pigment and an acrylate resin Of a mixed system having a lightness value of 2.5 at the time of color development and a lightness value of 8.9 at the time of color erasure, which is reversibly reversible into a color of about 40 μm by heat and a color of a fluorescent yellow pigment. A thermochromic layer,
The silver metallic luster layer 3 was the same as in Example 1. At 15 ° C. or lower, when the thermochromic layer develops a color and reflects light 5 which is a part of visible light of incident light and absorbs light 6 of other wavelengths, the laminate 1 has a silver metallic luster. When the thermochromic layer is decolored at 30 ° C. or higher, the silver metallic luster disappears and the color becomes a fluorescent yellow pigment. Reference numeral 9 denotes yellow light reflected by the thermochromic layer 7.

Example 7 In the laminate 1 of FIG. 2, the thermochromic layer 7 was composed of 1 part of 2-anilino-3-methyl-6-dibutylaminofluorane,
1,3-dimethyl-6-diethylaminofluoran 2
Part, bisphenol A 6 parts and neopentyl stearate 50 parts in a microcapsule form having an average particle diameter of 8 μm obtained by microencapsulation obtained by interfacial polymerization of an epoxy resin / amine-based curing agent. A mixture of a thermochromic material, a fluorescent pink pigment and an acrylate resin, having a lightness value of 2.3 at the time of color development and a lightness value of 5.5 at the time of color erasing with a thickness of about 40 μm by heat. And a thermochromic layer for reversibly decoloring to the color of a fluorescent pink pigment. The silver metallic luster layer 3 was the same as in Example 1. At a temperature of 15 ° C. or lower, the laminate 1 has a silver metallic glossy color, and at a temperature of 30 ° C. or higher, the silver metallic color disappears and becomes a fluorescent pink pigment color. Reference numeral 9 denotes pink light reflected by the thermochromic layer 7.

Example 8 In the laminate 1 shown in FIG. 2, the thermochromic layer 7 was made of a compatible solution of 3 parts of 2-anilino-3-methyl-6-dibutylaminofluorane, 6 parts of bisphenol A, and 50 parts of neopentyl stearate. Thermochromic material in the form of microcapsules having an average particle diameter of 8 μm obtained by microencapsulation of the thermochromic composition obtained by interfacial polymerization of an epoxy resin / amine-based curing agent, a fluorescent pink pigment, a blue pigment, and acrylic acid It is a mixed color of a fluorescent pink pigment and a blue pigment, which is formed by an ester resin and has a lightness of 2.4 μm and a lightness of 5.5 when the color is decolorized. This is a thermochromic layer that reversibly erases the color on the lavender, and the silver metallic luster layer 3 is the same as in Example 1. The laminate 1 includes:
At a temperature of 15 ° C. or lower, a silver metallic glossy color was obtained, and at a temperature of 30 ° C. or higher, the silver metallic color disappeared and a lavender color, which was a mixed color of a fluorescent pink pigment and a blue pigment, was obtained. 9 is a thermochromic layer 7
Shows the lavender colored light reflected by.

Example 9 In the laminate 1 shown in FIG. 2, the thermochromic layer 7 was made of a compatible solution of 3 parts of 2-anilino-3-methyl-6-dibutylaminofluorane, 6 parts of bisphenol A, and 50 parts of neopentyl stearate. Thermochromic material in the form of microcapsules having an average particle size of 8 μm obtained by microencapsulation of the thermochromic composition obtained by interfacial polymerization of an epoxy resin / amine-based curing agent, a blue pigment, a white pigment, and an acrylate resin And a pastel blue color, which is a mixed color of a blue pigment and a white pigment, having a color value of 2.2 μm and a lightness value of 5.4 when the color is decolorized. This is a thermochromic layer for reversibly decoloring to a color, and the silver metallic luster layer 3 was the same as in Example 1. The laminate 1 had a silver metallic luster color at 15 ° C. or lower, and had a silver metallic color disappearing at 30 ° C. or higher and had a pastel blue color which was a mixed color of a blue pigment and a white pigment. Reference numeral 9 denotes pastel blue light reflected by the thermochromic layer 7.

Embodiment 10 FIG. 3 shows an embodiment of the present invention.
This embodiment is a thermochromic laminate composed of three layers in which a coloring layer 8 as a third layer containing a non-thermochromic coloring agent is arranged next to the thermochromic layer 2. . The coloring layer 8 is a fluorescent orange layer having a thickness of about 10 μm and comprising a fluorescent orange pigment having a brightness value of 6.3 and an acrylate resin. At a temperature of 15 ° C. or less, the thermochromic layer develops color, reflects light 5 which is a part of visible light of incident light, and light 6 of other wavelengths.
Is absorbed, the color becomes a silver metallic glossy color. When the thermochromic layer is decolored at 30 ° C. or more, the silver metallic glossy color disappears and the color of the fluorescent orange pigment in the lower layer is obtained. 10 is a non-thermochromic coloring layer 8
Shows orange light reflected by.

Example 11 In the colored layer 8 of Example 10, a fluorescent red pigment having a lightness value of 4.7 was used in place of the fluorescent orange pigment, the lightness value at the time of color development was 2.2, and the lightness value at the time of decoloration was 2.2. A thermochromic composition comprising a compatibilizer of 3-part 2-anilino-3-methyl-6-dibutylaminofluoran having a brightness value of 9.0, 6 parts of bisphenol A, 25 parts of myristyl alcohol, and 25 parts of cetyl caprate was used. Average particle size of 8μm obtained by microencapsulation by interfacial polymerization of epoxy resin / amine type curing agent
Except for the second layer having a thickness of about 40 μm and comprising a thermochromic material in the form of microcapsules and an acrylate resin, the same as in Example 10. Below 20 ° C, the thermochromic layer develops color,
When the light 5 which is a part of the visible light of the incident light is reflected and the light 6 having the other wavelength is absorbed, the color becomes a silver metallic luster color,
When the thermochromic layer decolorizes at 20 ° C. or higher, the silver metallic luster color disappears, and the color of the fluorescent red pigment in the lower layer is restored. Reference numeral 10 denotes red light reflected by the non-thermochromic coloring layer 8.

Example 12 The procedure of Example 10 was the same as that of Example 10, except that a fluorescent pink pigment having a lightness value of 5.6 was used instead of the fluorescent orange pigment in the colored layer 8 of Example 10. Similarly, when the thermochromic layer develops a color at 20 ° C. or less, reflects light 5 which is a part of the visible light of incident light, and absorbs light 6 of other wavelengths, it becomes a silver metallic glossy color and becomes 20 ° C. When the thermochromic layer is decolorized,
The silver metallic luster disappears and becomes the color of the underlying fluorescent pink pigment. Reference numeral 10 denotes pink light reflected by the non-thermochromic coloring layer 8.

Example 13 The procedure of Example 10 was the same as that of Example 10, except that a fluorescent green pigment having a lightness value of 8.2 was used in place of the fluorescent orange pigment in the colored layer 8 of Example 10. Similarly, when the thermochromic layer develops a color at 20 ° C. or less, reflects light 5 which is a part of the visible light of incident light, and absorbs light 6 of other wavelengths, it becomes a silver metallic glossy color and becomes 20 ° C. When the thermochromic layer is decolored as described above, the silver metallic luster color disappears, and the color of the fluorescent green pigment in the lower layer is restored. Reference numeral 10 denotes green light reflected by the non-thermochromic coloring layer 8.

Comparative Example 1 In place of the thermochromic material of Example 1, the lightness value at the time of coloring was 4.0.
5. 2-anilino-3- having a lightness value at the time of decoloration of 6.0.
A thermochromic composition which is not colorless at the time of decolorization and is composed of a compatible solution of 6 parts of methyl-6-dibutylaminofluoran, 10 parts of bisphenol A and 25 parts of neopentyl stearate, is obtained by an interfacial polymerization method of an epoxy / amine curing agent. Example 1 is the same as Example 1 except that the thermochromic material in the form of microcapsules having an average particle size of 8 μm obtained by the chemical conversion is used. At 15 ° C. or lower, the thermochromic layer develops color, reflects light 5 which is a part of the visible light of incident light, and emits light 6 of other wavelengths.
When absorbed, it becomes a silver metallic luster color. In this comparative example, even if the thermochromic layer decolorizes at 30 ° C. or higher, the transmitted light 6 can still be sufficiently absorbed, so that the silver color becomes slightly thinner and still looks like a silver metallic glossy color.

Comparative Example 2 In the laminate 1 of FIG. 2, the thermochromic layer 7 was composed of 6 parts of 2-anilino-3-methyl-6-dibutylaminofluoran, 10 parts of bisphenol A, and neopentyl stearate 25.
Thermochromic composition obtained by microencapsulation of a thermochromic composition composed of a part of a compatibilizer, which does not become colorless when decolorized, by an interfacial polymerization method of an epoxy resin / amine-based curing agent, in the form of microcapsules having an average particle diameter of 8 μm And a mixed pigment composed of a blue pigment and an acrylate resin having a lightness value of 2.
5. A thermochromic layer having a thickness of about 40 μm and a lightness value of 3.3 at the time of decoloring, and the silver metallic luster layer 3 was the same as that in Example 1. In this comparative example, even if the thermochromic layer decolorizes at 30 ° C. or higher, the transmitted light 6 can still be sufficiently absorbed, so that the color becomes slightly bluish silver and still looks like a silver metallic luster color. .

Comparative Example 3 The brightness was changed to 3.7 instead of the fluorescent orange pigment of Example 10.
Example 10 is the same as Example 10 except that the red pigment layer of the colored layer 8 is used. Similarly, when the temperature is 15 ° C. or lower, the thermochromic layer develops a color, reflects light 5 which is a part of the visible light of incident light, and absorbs light 6 of other wavelengths, resulting in a silver metallic luster color. In this comparative example, even if the thermochromic layer decolorizes at 30 ° C. or higher, the transmitted light 6 can still be sufficiently absorbed, so that the color becomes slightly reddish silver and still looks like a silver metallic luster color. .

[0041]

Effects of the Invention The thermochromic laminate of the present invention reversibly changes its color from a silver metallic luster color to a colorless or non-thermochromic colorant used in combination with a change in temperature . In the present invention,
The function of the thermochromic material used is maintained as it is, and the function can be effectively exhibited. That is, in the color change, in a system in which a thermochromic layer is formed of a thermochromic material having an extremely small hysteresis width, the color changes in response to high sensitivity due to a temperature change, and a thermochromic material having an intermediate hysteresis width is applied. In such a system, the color changes in response to a change in temperature.
In a system in which a thermochromic layer is formed of a thermochromic material with an extremely large hysteresis width, the changed state is maintained at room temperature even after removing the heat or cold required for the color change. I can do it.

[Brief description of the drawings]

FIG. 1 is an explanatory view of a silver thermochromic laminate which is an example of the present invention.

FIG. 2 is an explanatory diagram of another embodiment.

FIG. 3 is an explanatory diagram of another embodiment.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 silver metallic luster thermochromic laminate 2 thermochromic layer 3 silver metallic luster layer 4 incident light 5 reflected light 6 transmitted light 7 thermochromic layer containing non-thermochromic colorant 8 non-thermochromic coloring layer 9 decolorization The light reflected by the thermochromic coloring layer 7 at the time 10 The light reflected by the non-thermochromic coloring layer 8 at the time of decoloration

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C09D 5/38 D02G 3/06 D02G 3/06 C09C 1/40 // C09C 1/40 C09D 5/00 C09D 5/00 B41M 5 / 18 101A

Claims (15)

(57) [Claims] 1. A. First Embodiment 16-39% by weight of natural mica surface
The optical thickness of the coating layer coated with titanium oxide is 110 to 110
A. a layer for adjusting the wavelength of reflected light, comprising a silver metallic glossy pigment having a particle size of 170 nm and a particle size of 5 to 100 μm, and a film forming material; A thermochromic material composed of an electron-donating compound, an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between the two. A thermochromic laminate that reversibly changes from silver metallic luster color to colorless, wherein a layer formed of a thermochromic material having a value of 8 or more and a film-forming material is a second layer. 2. A. The first layer is (a) the surface of natural mica
The coating layer coated with 6 to 39% by weight of titanium oxide has an optical thickness of 110 to 170 nm and a particle size of 5 to 100 μm.
m, a silver metallic glossy color coating layer formed by coating a coating composition comprising a silver metallic luster pigment, a film-forming material and a vehicle, and (b) a surface of natural mica having a weight of 16 to 39 wt. % Of titanium oxide and a silver metallic luster coloring sheet formed of a synthetic resin, and a reflection selected from a silver metallic luster pigment sheet having an optical thickness of 110 to 170 nm and a particle size of 5 to 100 μm. B. a layer for adjusting the wavelength of light; The second layer is (a) a thermochromic material comprising an electron-donating compound, an electron-accepting compound, and an organic compound medium which reversibly causes a color reaction between the two and has a lightness value of color density of 6 or less in a colored state. A layer formed by coating a colorless thermochromic material in a decolored state having a lightness value of 8 or more, a coating composition comprising a coating film forming material and a vehicle, and (b) an electron donating compound and electron accepting property A thermochromic material comprising a compound and an organic compound medium capable of reversibly causing a color reaction between the compound and a thermochromic material having a color density lightness value of 6 or less and a colorless lightness value of a decolorized state of 8 or more. The thermochromic laminate according to claim 1, which is a thermochromic sheet selected from a material and a synthetic resin, the thermochromic sheet being formed from a material and a synthetic resin. 3. The thermochromic layer of the second layer is a thermochromic material containing a non-thermochromic colored dye or pigment, and the lightness value (V1) of the color density of the mixed system at the time of color development is 6 or less. The color value (V2) of the mixed system at the time of decoloring is 4 or more and (V2)
3. The method according to claim 1, wherein-(V1)> 1.
A thermochromic laminate that reversibly changes from a silver metallic luster color to a dye pigment color. 4. The thermochromic layer of the thermochromic laminate according to claim 1, which reversibly changes from a silver metallic luster color to a colorless or dye pigment color. The lightness value (V3) of the color density formed by the non-thermochromic colored dye or pigment and the film forming material is 4 or more, and the lightness value (V3) of the thermochromic material at the time of color development is (V3). )-(V
4) A thermochromic laminate having a non-thermochromic dye / pigment coloring layer in which a relationship of> 1 is established and reversibly changing the color from a silver metallic luster color to a color of a dye / pigment. 5. The organophilic thermochromic material reversibly rise to color reaction of electron-donating compound and an electron-accepting compound and both
The thermochromic material according to any one of claims 1 to 4, wherein the thermochromic material is a thermochromic material in which the compound medium is encapsulated in microcapsules. Laminate. 6. The heat obtained by cutting and powdering the thermochromic laminate according to claim 1, which reversibly changes from a silver metallic luster color to a colorless or dye pigment color. Discolorable granules. 7. A thermochromic laminate which is reversibly changed from a silver metallic luster color to a colorless or dye pigment color according to any one of claims 1 to 5, and is cut into a thread. Discolorable thread. 8. A. 16-39% by weight of natural mica surface
The optical thickness of the coating layer coated with titanium oxide is 110 to 110
B. a coating composition comprising a silver metallic luster pigment having a particle size of 170 nm and a particle size of 5 to 100 μm, a coating film forming material, and a coloring agent; A lightness value of a color density of 6 or less and a colorless lightness value of a decolored state of 8 or more composed of an electron-donating compound, an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between the two. A thermochromic laminate that reversibly changes color from a silver metallic luster color to colorless by combining two types of coating compositions consisting of a thermochromic material, a film forming material, and a coloring agent. Two-pack type combination coating material for body formation. 9. A lightness value (V1) of the color density of a mixed system in which a coating composition comprising a thermochromic material, a coating film forming material, and a coloring agent is mixed with a non-thermochromic colored dye or pigment to form a color. ) Is 6
9. The reversibly silver color according to claim 8, wherein the color value of the mixed system at the time of decoloring is a thermochromic composition having a value (V2) of 4 or more and (V2)-(V1)> 1. Two-component combination for forming thermochromic laminates that change the color of metallic luster to the color of dyes and pigments
Paint material . 10. A. The optical thickness of the coating layer of natural mica coated with 16 to 39% by weight of titanium oxide is 110.
A coating composition comprising a silver metallic glossy pigment having a particle size of 5 to 100 µm, a particle size of 5 to 100 µm, a film-forming material and a vehicle; (A) A colorless lightness value of a colorless state in a colorless state of 6 or less and a colorless lightness value of an electron-donating compound, an electron-accepting compound, and an organic compound medium capable of reversibly causing a color reaction between them. A coating composition comprising a thermochromic material, a coating film forming material, and a coloring agent having a molecular weight of 8 or more; and (b) an organic compound that reversibly causes a color reaction between the electron-donating compound and the electron-accepting compound. A non-thermochromic colored dye for a thermochromic material, a film-forming material, and a colorant having a color density lightness value of 6 or less and a colorless lightness value of a decolored state of 8 or more composed of a compound medium. Alternatively, the lightness value (V1) of the color density of the mixed system at the time of color formation containing the pigment is 6 or less, and the lightness value (V2) of the mixed system at the time of decoloring is 4 or more (V2).
C.-a coating composition of (V1)> 1, and a thermochromic composition selected from: The lightness value (V3) of the color density formed by the non-thermochromic dye or pigment, the coating film forming material, and the colorant is 4 or more and between the lightness value (V4) of the thermochromic material at the time of color development. To (V
3) a coloring coating composition of a non-thermochromic dye / pigment in which the relation of-(V4)> 1 is satisfied; Three-component combination coating material for forming a thermochromic laminate that changes color. 11. A thermochromic material wherein an electron-donating compound and an electron-accepting compound and an organic compound which reversibly cause a color reaction between the two.
The thermochromic material according to any one of claims 8 to 10, which is a thermochromic material in which a compound medium is encapsulated in microcapsules, the thermochromic material reversibly changing from a silver metallic luster color to a colorless or dye pigment color. laminate for forming a union Align coating material. 12. A. The optical thickness of the coating layer of natural mica coated with 16 to 39% by weight of titanium oxide is 110.
B. a silver metallic gloss coloring sheet formed of a silver metallic gloss pigment having a particle size of 5 to 100 μm and a resin having a particle size of 5 to 100 nm; A lightness value of a color density of 6 or less and a colorless lightness value of a decolored state of 8 or more composed of an electron-donating compound, an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between the two. A thermochromic laminated sheet forming sheet that reversibly changes color from a silver metallic luster color to colorless by combining two types of sheets: a thermochromic material formed from a thermochromic material and a resin. 13. A thermochromic sheet comprising a thermochromic material and a non-thermochromic colored dye or pigment in addition to a thermochromic material having a color density lightness value (V1) of 6 or less at the time of color formation, The color value (V2) of the mixed system is 4 or more and (V2) −
The thermochromic sheet according to claim 12, which is a thermochromic sheet satisfying (V1)> 1 and reversibly changing from a silver metallic luster color to a dye pigment color. 14. A. The optical thickness of the coating layer of natural mica coated with 16 to 39% by weight of titanium oxide is 110.
B. a silver metallic gloss coloring sheet formed of a silver metallic gloss pigment having a particle size of 5 to 100 μm and a resin having a particle size of 5 to 100 nm; (A) A colorless lightness value of a colorless state in a colorless state of 6 or less and a colorless lightness value of an electron-donating compound, an electron-accepting compound, and an organic compound medium capable of reversibly causing a color reaction between them. A sheet formed of a thermochromic material having a color difference of 8 or more; and (b) a color-developed state comprising a synthetic resin and an electron-donating compound and an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between the two. The color density of a mixed system at the time of color development in which a non-thermochromic colored dye or pigment is blended in addition to a thermochromic material having a colorless lightness value of 6 or less and a decolorized colorless lightness value of 8 or more The lightness value (V1) of the mixed system at the time of decoloring is 6 or less and the lightness value (V2) of the mixed system is 4 or more and (V2) −
(V1) a sheet of> 1, a thermochromic sheet selected from the following: The non-thermochromic colored dye or pigment is mixed with the synthetic resin, and the lightness value (V3) of the color density is 4 or more, and the lightness value (V3) of the thermochromic material at the time of color development is (V3)- (V
4) A three-color combination sheet for forming a thermochromic laminate that reversibly changes color from a silver metallic luster color to a color of a dye and pigment, which is a combination of three types of colorant sheets that satisfy the relationship of> 1. 15. The thermochromic material wherein the electron-donating compound and the electron-accepting compound and an organic compound which reversibly cause a color reaction between the two.
The thermochromic material in which the compound medium is encapsulated in microcapsules, according to any one of claims 12 to 14,
A combination sheet for forming a thermochromic laminate that reversibly changes color from silver to colorless or dye pigment.