JP3172810B2 - 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 metallic glossy thermochromic laminate of metallic color and to coating compositions and sheets used to form the laminate. More specifically, a thermochromic laminate having a metallic glossy color that exhibits a color change from a metallic color of red, green, blue, and purple based on a temperature change, and a coating composition and a sheet used to form the laminate About.

[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 of metallic color from a metallic glossy color to colorless due to a temperature change, and a reversible color change to another different colored color, and a thermochromic material which clearly expresses the color change The material is not yet known. In addition, attempts to diversify the color change are based on actual fairness 3-1.
No. 4,400,400. 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 that is the selective scattering of visible light, so a blackish opaque layer is required on the back surface, and thus the color change is black-red-yellow-green-blue. -Because it looks purple-black, even if a pearlescent layer is provided thereon, the color change is not sharp. For example, when a metallic pearlescent pigment is used, its color change is as follows: metallic-metallic red-metallic yellow-metallic green-metallic blue-metallic purple- It becomes a metallic color and does not show a clear change to a color that does not have a metallic 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 the metallic color of metallic luster is a luxurious color and the change from the metallic color to another color attracts the attention of the viewer most, the demand for such a discoloring material has been great.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have conducted research to effectively exhibit the discoloration effect of a thermochromic material and to make the color change from metallic metallic gloss to vivid and colorful thermal discoloration, and completed the present invention. It was done. Unlike the liquid crystal, the thermochromic material used in the present invention has a distinctive color change in the thermochromic material itself, so that there is no need to provide a dark opaque layer as a lower layer, and the color-colorless change is possible. .
Therefore, by laminating the metallic-colored metallic luster pigment layer on the colored-colorless thermochromic layer made of the thermochromic material, a color change from the metallic metallic luster color to the colorless color can be visually recognized. Therefore, for example, by providing a colored-colorless thermochromic layer on a white support, and laminating a metallic metallic gloss layer on the thermochromic layer, it is possible to visualize a color change from metallic metallic gloss to white. I can do it.
Also, a clear color change from a metallic metallic glossy color to a colored color by mixing a non-discoloring colorant can be visually recognized by 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 metallic glossy color of the metallic color is clearly expressed in this manner, the present invention is widely used in the decoration field, the interior field, the toy, the stationery, and the information field.

[0005]

Means for Solving the Problems The present invention provides: "1. A. A coating layer in which the surface of natural mica is coated with 45 to 58% by weight of titanium oxide has an optical thickness of 245 to 415.
B. a layer for adjusting the wavelength of reflected light, comprising a metallic metallic luster pigment having a particle size of 5 to 60 μm and a film forming material, the first layer comprising: 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 which reversibly changes from a metallic metallic gloss to a colorless color, 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) a surface of natural mica of 45 to 58
The optical thickness of the coating layer coated with wt.
A metallic color metallic glossy color coating layer formed by coating a coating composition comprising a metallic color metallic gloss pigment having a particle size of 45 to 415 nm and a particle size of 5 to 60 μm, a film forming material, and a coloring agent; (B) 45 to 58% by weight of natural mica surface
The optical thickness of the coating layer coated with titanium oxide of
B. a layer for adjusting the wavelength of reflected light selected from a metallic metallic gloss pigment having a particle size of 415 nm and a particle size of 5 to 60 μm and a metallic metallic gloss color sheet molded with a synthetic resin; 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 item 1, which is a thermochromic layer selected from a material and a synthetic resin, which is a thermochromic sheet selected from the group consisting of a material and a synthetic resin. 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 metallic metallic luster color to a color of a dye or pigment, as described in the item 1 or 2, wherein> 1. 4. The thermochromic layer of the thermochromic laminate which reversibly changes from a metallic metallic color to a colorless or dye pigment color as described in any one of Items 1 to 3, followed by non-thermochromic property 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 the lightness value (V3)-(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 metallic metallic luster color to a dye / pigment color. 5. Metallic metallic luster pigment on natural mica surface
Coated with 5 to 58% by weight of titanium oxide, and 0.5
The optical thickness of the coating layer coated with 10 to 10% by weight of the non-thermochromic colored dye / pigment is 245 to 415 nm, and the particle size is 5 to 60.
5. The thermochromic laminate according to any one of items 1 to 4, which is a metallic metallic luster pigment of μm, which reversibly changes from a metallic metallic luster color to a non-thermochromic dye pigment color. 6. The metallic luster pigment of any one of claims 1 to 5, wherein the metallic luster pigment is a metallic red luster pigment having an optical thickness of 245 to 275 nm, in which the surface of natural mica is coated with 45 to 47% by weight of titanium oxide. A thermochromic laminate which reversibly heat-discolors from a metallic red metallic luster color to a colorless or non-thermochromic dye / pigment described in the above item. 7. 6. The metallic luster pigment according to any one of claims 1 to 5, wherein the metallic luster pigment is a metallic purple luster pigment having an optical thickness of 280 to 310 nm obtained by coating the surface of natural mica with 48 to 50% by weight of titanium oxide. 3. A thermochromic laminate which reversibly heat-discolors from a metallic purple metallic luster color to a colorless or non-thermochromic dye / dye described in the above item. 8. 7. The metallic luster pigment of any one of 1 to 5, wherein the metallic luster pigment is a metallic blue luster pigment having an optical thickness of 315 to 350 nm in which the surface of natural mica is coated with 51 to 54% by weight of titanium oxide. 4. A thermochromic laminate which reversibly heat-discolors from a metallic blue metallic luster color to a colorless or non-thermochromic dye / dye described in the above item. 9. 6. The metallic luster pigment of any one of claims 1 to 5, wherein the metallic luster pigment is a metallic luster pigment having an optical thickness of 375 to 415 nm, wherein the surface of natural mica is coated with 55 to 58% by weight of titanium oxide. The thermochromic laminate which reversibly heat-discolors from a metallic green metallic luster color to a colorless or non-thermochromic dye described in 1). 10. Item 1. The thermochromic material according to any one of items 1 to 9, wherein the thermochromic material is a thermochromic material obtained by encapsulating an organic compound medium that reversibly causes a color reaction between the electron-donating compound and the electron-accepting compound and both. The thermochromic laminate according to any one of the preceding claims, which reversibly changes from a metallic color to a colorless or dye-colored color. 11. A metallic metallic luster pigment coats the surface of natural mica with 45 to 58% by weight of titanium oxide,
The optical thickness of the coating layer coated with 0% by weight of iron oxide is 24
Any one of Items 1 to 10, which is a metallic luster pigment having a metallic color of 5 to 415 nm and a particle size of 5 to 60 μm.
A thermochromic laminate which reversibly changes from a metallic metallic luster color to a pale yellow color as described in the above item. 12. 12. A thermochromic granule obtained by cutting and powdering a thermochromic laminate which reversibly changes from a metallic metallic luster color to a colorless or dye pigment color according to any one of items 1 to 11. . 13. 11. A thermochromic yarn formed by cutting a thermochromic laminate reversibly changing from a metallic metallic luster color to a colorless or dye pigment color as described in any one of 1 to 10 to form a thread. 14． A. The optical thickness of the coating layer obtained by coating the surface of natural mica with 45 to 58% by weight of titanium oxide is 245 to 415.
B. a coating composition comprising a metallic metallic luster pigment having a particle size of 5 to 60 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. thermochromic material and a film-forming material exhibition colorant and is
A two-pack type combination coating material for forming a thermochromic laminate that reversibly changes from a metallic metallic color to colorless by combining two types of coating compositions comprising: 15. 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. A thermochromic composition having a color value (V2) of 4 or more at the time of decoloration and having a value of (V2)-(V1)> 1.
Two-pack type assembly for forming a thermochromic laminate that reversibly changes from a metallic metallic luster color to a dye / pigment color described in paragraph
Coating materials . 16. A. The optical thickness of the coating layer obtained by coating the surface of natural mica with 45 to 58% by weight of titanium oxide is 245 to 415.
B. a coating composition comprising a metallic metallic luster pigment having a particle size of 5 to 60 μm, a coating film forming material, and a vehicle; (A) a colorless lightness value of a colorless state in a color-developed state of 6 or less, in which a color reaction between the electron-donating compound and the electron-accepting compound is reversibly induced to form a color formed of an organic compound medium; 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. When a non-thermochromic colored dye or pigment is blended with a thermochromic material having a colorless lightness value of 6 or less and a decolorized colorless lightness value of 8 or more composed of a compound medium and a colorless state. A coating composition wherein the lightness value (V1) of the color density of the mixed system is 6 or less and the lightness value (V2) of the mixed system at the time of decoloring is 4 or more and (V2)-(V1)>1; A thermochromic composition selected from C.I. 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 reversible metallic color from a metallic luster color obtained by combining three types of overcoating compositions of a non-thermochromic dye / pigment coloring coating composition satisfying the relationship of-(V4)> 1. Three-part combination for the formation of thermochromic laminates that change color to pigment
Paint material . 17． Item 14. The thermochromic material according to item 14 to 16, 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 coating material for forming a thermochromic laminate, which reversibly changes color from a metallic color to a colorless or pale yellow color or a color of a dye or pigment, according to any one of the preceding claims. 18. A metallic metallic luster pigment coats the surface of natural mica with 45 to 58% by weight of titanium oxide,
The optical thickness of the coating layer coated with 0% by weight of iron oxide is 24
A metallic luster pigment of 5 to 415 nm and a particle size of 5 to 60 μm or a natural mica is coated with 45 to 58% by weight of titanium oxide, on which 0.5 to 10% by weight of non-thermal discoloration is applied. The optical thickness of the coating layer coated with the chromatic coloring pigment is 245 to 415 nm, and the particle size is 5 to 60 μm.
Item 18. The thermochromic laminate according to any one of Items 14 to 17, which is a metallic luster pigment having a metallic color of m, and which reversibly changes from a metallic luster color of a metallic color to a pale yellow color or a dye / pigment color. Combination coating material for forming. 19. A. The optical thickness of the coating layer obtained by coating the surface of natural mica with 45 to 58% by weight of titanium oxide is 245 to 415.
B. a metallic metallic gloss coloring sheet formed of a metallic metallic gloss pigment having a particle size of 5 to 60 μm and a synthetic resin, and B. 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-forming sheet that reversibly changes color from a metallic metallic luster color to colorless by combining two types of thermochromic material and a thermochromic sheet molded with a synthetic resin. 20. 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 19, which is a thermochromic sheet, which is reversibly changed from a metallic metallic luster color to a dye pigment color. 21. A. The optical thickness of the coating layer obtained by coating the surface of natural mica with 45 to 58% by weight of titanium oxide is 245 to 415.
B. a metallic metallic gloss coloring sheet formed of a metallic metallic gloss pigment having a particle size of 5 to 60 μm and a synthetic resin, and B. (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. And (b) a color density in a color-developed state comprising: a sheet formed from a thermochromic material having a molecular weight of 8 or more; and (b) an organic compound medium that reversibly causes a color reaction between the electron-donating compound and the electron-accepting compound. The lightness value of the color density of a mixed system in which a non-thermochromic colored dye or pigment is blended in addition to a thermochromic material having a lightness value of 6 or less and a colorless lightness value in a decolored state of 8 or more, (V1) is 6 or less, the color value (V2) of the mixed system at the time of decoloring is 4 or more, and (V2)-(V1)>
C. 1 sheet, a thermochromic sheet selected from: The lightness value (V3) of the color density in which a non-thermochromic colored dye or pigment is blended is 4 or more, and between the lightness value (V4) of the thermochromic material at the time of color development, and (V3)-(V4). A three-way combination sheet for forming a thermochromic laminate that reversibly changes from a metallic 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. 22. Item 14. The thermochromic material according to item 14 to 16, 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 from a metallic color to a colorless or pale yellow color or a color of a dye or pigment, according to any one of the preceding claims. 23. A metallic metallic luster pigment coats the surface of natural mica with 45 to 58% by weight of titanium oxide,
The optical thickness of the coating layer coated with 0% by weight of iron oxide is 24
A metallic luster pigment of 5 to 415 nm and a particle size of 5 to 60 μm or a natural mica is coated with 45 to 58% by weight of titanium oxide, on which 0.5 to 10% by weight of non-thermal discoloration is applied. The optical thickness of the coating layer coated with the chromatic coloring pigment is 245 to 415 nm, and the particle size is 5 to 60 μm.
23. The thermochromic laminate according to any one of items 19 to 22, which is a metallic luster pigment having a metallic color of m, which reversibly changes from a metallic luster color of a metallic color to a pale yellow color or a dye / pigment color. Forming sheet. About.

The metallic luster pigment of the metallic color used in the present invention is, specifically, a pigment exhibiting a metallic color in which the surface of natural mica particles is coated with titanium oxide. A pigment in which a titanium oxide layer is coated with iron oxide is also used.
Further, a dichroic metallic luster pigment coated with a non-thermochromic colored dye on the titanium oxide coating is also used. The term "metallic color" as used in the present invention refers to a metallic luster color of red, green, blue or purple.

More specifically, the metallic metallic luster pigment has a surface of natural mica particles coated with 45 to 58% by weight of titanium oxide.
Optical thickness of coating layer 245 to 415 nm, particle size 5 to 60
μm of natural mica particles, the surface of which is coated with 45 to 58% by weight of titanium oxide and further coated with 4 to 10% by weight of iron oxide. ６０60 μm are also used. The optical thickness of the coating layer is 245 to 415 nm, in which the surface of the natural mica particles is coated with 45 to 58% by weight of titanium oxide, and the upper layer is coated with 0.5 to 10% by weight of a non-thermochromic colored dye. , Particle size 5
Dichroic metallic luster pigments of 〜60 μm can also be used.

[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 245-415 nm titanium oxide layer formed on the surface of natural mica spectrally selects and reflects 380-700 nm purple-red light. For 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. The lightness values at the time of thermochromic material development and decoloration are the achromatic array, where complete black is set to 0 and complete white is set to 10 so that the difference in brightness perception is evenly spaced between them The chromatic lightness indicates an achromatic lightness value in which the sensation of the chromatic color brightness is equal to this value.
That is, the smaller the brightness value, the closer to black, and the higher the brightness value, the closer to white.

[0009]

The heat-modified laminate of the present invention is a laminate in which a metallic color metallic luster pigment layer is laminated on a thermochromic layer, and the color change of the thermochromic layer is passed through the metallic color metallic luster pigment layer. This is to make the viewer see. As described above, mica coated with titanium oxide disperses visible light of red to purple into light of each color wavelength according to the coating weight of the titanium oxide and the optical thickness of the coating, and emits only light of a specific wavelength. It has the effect of reflecting and transmitting other light. On the other hand, mica does not diffusely reflect light but reflects parallel light, so the light has a metallic luster. Light transmitted through the first layer is absorbed by the thermochromic layer of the second layer. In this way, the metallic luster light of a specific wavelength is reflected, so that the metallic color becomes a specific color. Specifically, mica has the effect of changing the wavelength of the reflected light at the time of interference by adjusting the coating amount of the coated titanium oxide, that is, the thickness of the coating layer. For example, a titanium oxide-coated mica whose optical thickness has been adjusted so as to selectively reflect light of a specific color and transmit light of other colors, the transmitted light is absorbed by the underlying black, and the specific color light Since only the light is reflected, a specific metallic color is exhibited. On the other hand, when the base is white, the transmitted light is also reflected by the white of the base, and reflects not only the metallic color light but also other color lights and reflects all the wavelengths of visible light, so that the white light is perceived as white. You. Therefore, by changing the lower thermochromic layer reversibly from black to white, the viewer can visually recognize the reversible color change from a specific metallic color to white.

What is important here is that titanium oxide must satisfy the requirement of an optical thickness of 245 to 415 nm.

When the optical thickness of the titanium oxide coated on the natural mica is within the above range, the light is reflected in each of red to purple colors corresponding to the thickness, and the reflected light becomes parallel rays, so that the metallic color light is emitted. Becomes For example, coating weight% of titanium oxide
Are 45-47% and have an optical thickness of 245-275 nm, which transmit green light of 500-550 nm,
Reflects ~ 700 nm red light. When light transmitted through the metallic pigment layer is absorbed by the thermochromic material layer therebelow, only the red metallic color is seen by the viewer.

When the thermochromic agent layer reflects the light transmitted through the metallic pigment layer, all visible rays can be seen as it is by the eyes of the viewer, so that the thermochromic layer looks white. Disappearance and expression are reversible. Since the particles of mica are arranged in parallel layers, the reflected light is not irregularly reflected but is a parallel light beam. Since such parallel reflected light has a metallic luster color, the reflected light of this pigment becomes red light with metallic luster, that is, a red metallic color.

Similarly, the coating weight percentage of titanium oxide is 55 to 55%.
58% pigment with an optical thickness of 375-415 nm is 63
Transmits red light of 0 to 700 nm and 500 to 540 n
The m green light is reflected and becomes a green metallic color.

The coating weight percentage of titanium oxide is 51 to 5%.
4% pigment with an optical thickness of 315-350 nm is 580
630 nm orange light, 430-500 nm
Blue light is reflected and becomes a blue metallic color.

A pigment having a coating weight percentage of titanium oxide of 48 to 50% and an optical thickness of 280 to 310 nm is 530 to 58.
It transmits yellow light of 0 nm and reflects violet light of 380 to 430 nm to form a purple metallic color.

As described above, the present invention reflects light of a specific wavelength depending on the coating amount of a specific titanium oxide and the optical thickness, and has a metallic color due to an interference effect of mica and a colorless colorless discoloration effect of a thermochromic material. Can be expressed.

Furthermore, in a metallic metallic luster pigment in which the surface of natural mica particles is coated with titanium oxide and the upper layer is coated with iron oxide, in addition to the above-described wavelength-selective reflection and transmission effects, the iron oxide itself has By adding the characteristic of absorbing violet light and reflecting yellow light, the reversible color change from metallic to pale yellow can be seen. If the coverage of titanium oxide is less than 45% by weight, it is difficult to produce a sufficient metallic color. Further, when the coverage of titanium oxide exceeds 58% by weight, the wavelength selectivity is deteriorated, so that a sufficient metallic color is not obtained. When the coverage of iron oxide is less than 4% by weight, the effect of the above-mentioned iron oxide is not sufficiently exhibited, and when it exceeds 10% by weight, a metallic color is obtained. No color change from a metallic color. When iron oxide is used in combination, forming an iron oxide film on a titanium oxide film is most effective for developing a color change from a metallic metallic glossy color to a pale yellow color. When the titanium oxide is coated on the iron oxide, the reflection effect of the titanium oxide is large, so that the effect of the iron oxide is small. When titanium oxide and iron oxide coexist, the reflection efficiency of iron oxide deteriorates because titanium oxide may block the reflected light of iron oxide as compared with the case where iron oxide is in the upper layer. When an iron oxide film is provided on the titanium oxide film, the iron oxide layer has the property of absorbing violet light and reflecting other light, and since this light looks yellow, it has a metallic luster due to the titanium oxide layer It has the effect of changing the color from light yellow. This is because the reflected light from the iron oxide layer is not blocked or reflected by other layers due to the presence of the iron oxide film in the upper layer.

[0018] In addition, among metallic metallic luster pigments in which the surface of natural mica particles is coated with titanium oxide and the upper layer is coated with a non-thermochromic colored pigment, the non-thermochromic colored pigment to be coated is used. Depending on the color, a wide variety of color changes can be expressed, for example, in combination with a black ← → white thermochromic layer, a metallic color ← → pink, a metallic color ← → blue, etc. → The reversible color change of color can be visualized. When the coating ratio of titanium oxide is less than 45% by weight, a sufficient metallic color is hardly produced, and therefore, when coated with a non-thermochromic coloring dye, the metallic color does not appear. On the other hand, when the coverage of titanium oxide exceeds 58% by weight, the wavelength selectivity is deteriorated, so that it does not appear to have a sufficient metallic color. When the coverage of the non-thermochromic coloring dye is less than 0.5% by weight, a sufficient color density cannot be obtained. If it exceeds 10% by weight, the color density of the colored color is too high, and the contrast between the metallic color and the color becomes small. When each pigment is within the above-mentioned range, it is possible to selectively transmit light having a wavelength of a metallic color and reflect light having a wavelength having a complementary color relationship. If the wavelength is outside the above range, the wavelength selectivity is lost, or the color does not become a metallic color even though there is wavelength selectivity.

When a layer containing a non-color-changing dye / colorant is used as the thermochromic layer, a reversible color change from a metallic metallic glossy color to a colored colorant can be visually recognized. Since the metallic luster pigment layer of a metallic color is transparent, if a non-discoloring colored layer is arranged as a lower layer, the color of this colored layer can be visually recognized simultaneously with the thermal discoloration of the thermochromic layer. When a non-thermochromic coloring layer is disposed as the lowermost layer, the lower non-chromatizing coloring layer such as characters and patterns are concealed in the coloring state of the thermochromic layer. The reflection effect enhances the concealing effect compared to the concealing effect of only thermal discoloration.

As described above, the thermochromic layer comprises three components: an electron-donating color-forming compound, an electron-accepting compound, and an organic compound medium. Specifically, for example, the aforementioned Japanese Patent Publication No. 51-35414
(A) an electron-donating color-forming organic compound, (b) a compound having a phenolic hydroxyl group, and (c) a linear aliphatic monovalent having no polar substituent. A reversible thermochromic material containing three components of alcohol as essential components. Or (2) (a) 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 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, (c) a higher aliphatic monohydric alcohol having no polar substituent, and an alicyclic monomer having no polar substituent. The essential component is a compound selected from carboxylic acid and a compound having no polar substituent obtained from a linear aliphatic monohydric alcohol having no polar substituent, and this is used as a microcapsule. Includes 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. And a thermochromic material obtained by dissolving or dispersing the same in a vehicle. And so on.

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.

In addition, a thermochromic material containing a color-memorizing thermochromic dye which exhibits a large hysteresis characteristic and which changes color, 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 laminate of the present invention will be specifically described. The thermochromic laminate of the present invention comprises (A) a laminate obtained by laminating a metallic luster pigment layer on a thermochromic layer, and (B) a thermochromic material obtained by mixing a non-chromogenic dye with a thermochromic material. A laminate in which a metallic luster pigment layer of a metallic color is laminated on the layer,
(C) A laminate in which a thermochromic layer is laminated on a non-chromogenic coloring layer, and a metallic metallic pigment layer of a metallic color is laminated on the thermochromic layer.

The thermochromic laminate may be laminated on a support, a transparent protective film may be laminated on the metallic metallic luster pigment layer, or the thermochromic layer and the metallic metallic luster may be laminated. A clear coat layer or a transparent laminate layer may be interposed between the pigment layer and the pigment layer. Next, the metallic glossy thermochromic laminate of the metallic color of the present invention is described in the above (A) to (A).
A description will be given based on (C). In the laminate (A) described above, the metallic luster pigment layer of the metallic color has a particle size of about 5 to 6
A layer in which a metallic luster pigment having a metallic color of 0 μm is fixed in a dispersed state in a transparent resin, and a thermochromic layer is an electron-donating color-forming organic compound, an electron-accepting compound. A thermochromic material consisting of a three-component homogeneous compatibilizer of an organic compound medium (hereinafter referred to as a thermochromic material), which is fixed in a dispersed state with a transparent film-forming material, A layer having a color density lightness value of 6 or less and a colorless lightness value of a decolored state of 8 or more. The layer has a reversible color change from a metallic metallic gloss to a colorless, or from a colorless to metallic metallic gloss. A metallic glossy thermochromic laminate having a metallic color to be exhibited is constituted. 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 metallic metallic luster pigment in the upper layer. For example, in the case of a metallic metallic luster pigment, the metallic metallic pigment is clearly metallic. It looks like a metallic luster color. However, when the lightness value of the color development state exceeds 6, the light transmitted through the metallic luster pigment of the metallic color cannot be sufficiently absorbed, and a part of the light is reflected again, so that the metallic 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 metallic metallic luster pigment, so that the light reflected by the metallic metallic luster pigment and the thermochromic material The light reflected by is mixed and returned to white light, so it looks colorless. However, when the lightness value in the decolored state is less than 8, the light transmitted through the metallic luster pigment of the metallic color cannot be sufficiently reflected and becomes partially colorless due to partial absorption, and the metallic color in the colored state remains.

In the laminate of (B), the metallic luster pigment layer of the metallic color is a layer in which a metallic luster pigment of about 5 to 60 μm is fixed in a transparent resin in a dispersed state. When the thermochromic material and the non-color-changing colorant (dye, pigment) are mixed, the lightness value (V ₁ ) of the color density in the color-developing state is 6 or less, and the lightness value (V ₂ ) of the color in the decoloring state
Is 4 or more, and the lightness value (V ₂ ) ... lightness value (V
₁ ) A layer which satisfies the relationship of> 1, and forms a metallic metallic thermochromic laminate having a reversible color change from metallic to colored and from colored to metallic. 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 lightness value (V ₂ ) of the mixed color system in the decolored state is 4 or more, and V ₂ −V 1> 1
The reason is that in this system, a non-color-changing colorant, a non-thermochromic dye, and a pigment are mixed to form a color, so that the lightness value becomes small and varies depending on the color of the dye / 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 one greater than the lightness value in the colored state.
If it is less than 1, the contrast is too small and the color change is not clear. If there is a lightness value of 4 or more under such conditions, for example, a reversible color change from a metallic color to a color and from a colored to a metallic color can be exhibited. But 4
If it is less than 3, the color density of the underlying color mixture layer becomes too dark, and the metallic color is seen even in the decolored state.

In the layered product of (C), the lightness value (V ₃ ) of the color density is 4 or more below the thermochromic layer, and is between the lightness value (V ₄ ) of the color developing state of the thermochromic layer. , _V 3 _-V 4>
A non-color-changing colored layer satisfying the relationship 1 is formed, and a metallic metallic gloss-colored thermochromic laminate exhibiting a reversible color change between the metallic metallic gloss color and the color of the non-color-changing colored layer is formed. Be composed. Incidentally, the thermochromic material described above, the smaller the lightness value at the time of decoloring, the closer to black, the larger the lightness value,
Because it is close to white, it can be used as an index of how much visible light is absorbed and how much it is reflected.This index is based on the thermochromic layer under which visible light transmitted through the metallic metallic luster pigment layer is located. Shows how to reflect and absorb.

Therefore, if the thermochromic layer has a lightness value of 6 or less, the thermochromic layer has sufficient ability to absorb visible light transmitted through the metallic metallic luster pigment, and as a result, is reflected by the metallic metallic luster pigment layer. Since only metallic light is visible, it looks metallic. On the other hand, when the brightness value is 8 or more, the visible light transmitted through the metallic luster pigment layer is reflected, so that the metallic light reflected by the metallic luster pigment layer is reflected by the thermochromic layer. To see both of the light
Invisible in metallic colors.

That is, it is an index as to whether or not the material has a characteristic in which it looks like a metallic color below the discoloration temperature of the thermochromic material and disappears above the discoloration temperature. The lightness value of the present invention is a value obtained by measuring a sample adjusted as described below using an IC-3600 color difference meter manufactured by Tokyo Denshoku Co., Ltd. 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.
The thermochromic laminate of the present invention comprises a layer in which the above-mentioned metallic luster pigment of a metallic color and a thermochromic material are bonded by a transparent film-forming material.

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. Acetate cellulose, nitrate cellulose,
Cellulose derivatives such as ethyl cellulose. 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 Soluble synthetic resins such as water-soluble alkyd resins, water-soluble melamine resins, water-soluble urea resins, water-soluble phenol resins, water-soluble epoxy resins, water-soluble polybutadiene resins, and cellulose derivatives in water and organic solvents Or dispersed composition is used.
In addition, each layer of the thermochromic laminate of the present invention also includes a molded sheet in which each pigment or thermochromic material is mixed with a synthetic resin. 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. A laminate may be formed by using a sheet and a coating film in combination.

It is preferable to use a transparent resin for the metallic luster pigment layer. The laminate can be formed on the surface of the base material, or can be formed as a laminate using no base material.

As the substrate, in addition to various films and sheets, the surface of the molded article itself is used. That is, a thermochromic laminate can be formed on the surface of the molded article to obtain a thermochromic molded article. The base material is paper, synthetic paper, cloth, non-woven fabric,
Synthetic leather, leather, plastic, glass, ceramics, metal, wood, stone and the like are used. Also, it is not limited to a planar shape,
Those having a processed surface such as unevenness or fiber shape can also 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, brushing, spray coating, electrostatic coating, electrodeposition coating. , Flow coating, roller coating, dip coating, and the like. Further, it can be formed into a film sheet by extrusion molding or the like and bonded together, or a thermochromic layer and a metallic luster pigment layer can be obtained by multilayer molding.

Incidentally, ultraviolet absorbers, infrared absorbers, antioxidants, singlet oxygen quenchers, antioxidants, antistatic agents, polarizers, thixotropic agents, defoamers, stabilizers, plasticizers, Addition of a flame retardant, extender, lubricant, foaming agent and the like can be added to each layer such as a clear coat layer, a metallic luster pigment layer, and a thermochromic layer as needed.

[0035]

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. No. 3 is a natural mica whose surface is coated with 47% by weight of titanium oxide, has an optical thickness of 265 nm, and a metallic red metallic luster pigment having a particle size of 10 to 60 μm and an acrylic ester resin having a thickness of about 40 μm.
This layer has an effect of adjusting the wavelength of the 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. 2 is a thermochromic composition comprising a compatibilizer of 3-anilino-3-methyl-6-dibutylaminofluorane, 3 parts of bisphenol A, and 50 parts of neopentyl stearate. In the form of microcapsules having an average particle size of 8 μm obtained by microencapsulation by a synthetic method, a thermochromic material A having a lightness value of 2.2 at the time of color development and a lightness value of 9.0 at the time of decolorization and an acrylate resin are used. This is a second layer having a thickness of about 40 μm, and reversibly develops and decolors by heat. When the thermochromic layer develops color at 15 ° C. or less, reflects light 55 having a wavelength of 650 to 700 nm, which is a part of incident light, and absorbs light 6 having other wavelengths,
It becomes a metallic red metallic luster color, and at 30 ° C. or higher, the thermochromic layer is decolorized, and when transmitted light 6 is reflected, all incident light is reflected, and the metallic red metallic luster color disappears and becomes colorless. Was.

Example 2 In place of the metallic red metallic luster pigment of Example 1, the surface of natural mica was coated with 48% by weight of titanium oxide. The metallic purple metal having an optical thickness of 295 nm and a particle size of 10 to 60 μm. Example 1 was the same as Example 1 except that a gloss pigment was used. The color of the thermochromic layer develops below 15 ° C,
When light 5 having a wavelength of 380 to 430 nm, which is a part of the incident light, is reflected and light 6 having other wavelengths is absorbed, the color becomes a metallic purple metallic luster, and the thermochromic layer decolorizes at 30 ° C. or higher. When the transmitted light 6 was reflected, all of the incident light was reflected, and the metallic purple metallic luster disappeared and became colorless.

Example 3 In place of the metallic red metallic luster pigment of Example 1, the surface of natural mica was coated with 52% by weight of titanium oxide, and the metallic thickness was 330 nm. Example 1 except that a gloss pigment was used
And the same. At 15 ° C. or lower, the thermochromic layer develops a color, reflects light 5 having a wavelength of 430 to 500 nm, which is a part of incident light, and absorbs light 6 having other wavelengths, resulting in a metallic blue metallic luster color. When the thermochromic layer was decolored at 30 ° C. or higher and reflected the transmitted light 6, all of the incident light was reflected, and the metallic blue metallic luster disappeared and became colorless.

Example 4 In place of the metallic red metallic luster pigment of Example 1, the surface of natural mica was coated with 57% by weight of titanium oxide, and the metallic thickness was 395 nm, and the metallic green metal had a particle size of 10 to 60 μm. Example 1 was the same as Example 1 except that a gloss pigment was used. At 15 ° C. or lower, the thermochromic layer develops a color, reflects light 5 having a wavelength of 500 to 540 nm, which is a part of incident light, and absorbs light 6 having other wavelengths. When the thermochromic layer was decolored at 30 ° C. or higher and reflected the transmitted light 6, all the incident light was reflected, and the metallic green metallic gloss disappeared and became colorless.

Example 5 The same procedure as in Example 1 was repeated except that 2-anilino-3-methyl-6-dibutylaminofluorane was replaced by 1.5 parts of 6-diethylamino-benzo (a) -fluorane. Example 1 was the same as Example 1 except that a thermochromic material having a lightness value of 4.2 and a lightness value at the time of decoloring of 8.8 was used. Similarly 1
Below 5 ° C, the color becomes metallic magenta and 30 ° C
Above, the metallic magenta color disappeared and became colorless.

Example 6 1.5 parts of 6-diethylamino-benzo (a) -fluorane was used in place of 2-anilino-3-methyl-6-dibutylaminofluoran of Example 2 and 3- (4-diethylamino- 2-ethoxyphenyl) -3- (1-ethyl-2
-Methylindol-3-yl) -4-azaphthalide (0.5 part), and a color value of 3.8 prepared in the same manner as described above;
Example 2 was the same as Example 2 except that a thermochromic material C having a lightness value of 8.7 at the time of decoloring was used. Similarly, at 15 ° C. or lower, the color became metallic purple, and at 30 ° C. or more, the metallic purple color disappeared and became colorless.

Example 7 3- (4-diethylamino-2) was used in place of 2-anilino-3-methyl-6-dibutylaminofluoran of Example 3.
-Ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide 0.5 part, prepared in the same manner as described above, for the color value 3.4 at the time of color development and the lightness value at the time of decolorization. Example 3 except that the thermochromic material of 8.8 was used.
And the same. Similarly, at 15 ° C. or lower, the color became metallic blue, and at 30 ° C. or more, the metallic blue color disappeared and became colorless.

Example 8 In place of 2-anilino-3-methyl-6-dibutylaminofluoran of Example 4, 0.5 part of 3,3-di (4-diethylamino-2-ethoxyphenyl) 4-azaphthalide was used. Example 4 was the same as Example 4 except that the amount of the thermochromic material, which was prepared in the same manner and had a color value of 5.1 and a color value of 8.9, was used. Similarly, at 15 ° C. or lower, the color became metallic green, and at 30 ° C. or more, the metallic green color disappeared and became colorless.

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 diameter 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 ester A pastel blue, which is a mixed color of a blue pigment and a white pigment, which is a mixture of a blue pigment and a white pigment having a lightness value of 2.5 when the mixed system is made of a resin and having a lightness value of 8.9 when the color is decolored and a lightness value of 8.9 when the color is erased This is a thermochromic layer that reversibly erases the color and the metallic color metallic luster layer 3 is the same as in Example 1. The laminate 1
When the temperature is 15 ° C. or lower, the thermochromic layer develops color, reflects light 5 of 650 to 700 nm, which is a part of incident light, and absorbs light 6 of other wavelengths. When the thermochromic layer was decolored at 30 ° C. or higher, the metallic red metallic luster color disappeared and became a pastel blue color that 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.

Example 10 In the laminate 1 shown in FIG. 2, the thermochromic layer 7 was made of a heat-resistant material comprising 1.5 parts of 6-diethylamino-benzo (a) -fluorane, 6 parts of bisphenol A, and 50 parts of neopentyl stearate. The thermochromic material is a microcapsule having an average particle diameter of 8 μm obtained by microencapsulation of the discolorable composition by an interfacial polymerization method of an epoxy resin / amine-based curing agent, a fluorescent orange pigment, and an acrylate resin. ,
A thermochromic layer in which the mixed system has a lightness value of 4.5 at the time of color development and a lightness value of 6.1 at the time of color erasing, and has a thickness of about 40 μm and is capable of reversibly performing color development by heat and decoloring to the color of a fluorescent orange pigment. The metallic color metallic luster layer 3 was the same as in Example 1. At a temperature of 15 ° C. or less, the thermochromic layer develops a color, and the laminated body 1 emits light 650 to 700 nm, which is a part of the incident light.
Is reflected and absorbs light 6 of other wavelengths, it becomes a metallic red metallic luster color. When the thermochromic layer is decolored at 30 ° C. or more, the metallic red metallic luster color disappears and the color of fluorescent orange pigment It became. Reference numeral 9 denotes orange light reflected by the thermochromic layer 7.

Example 11 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. 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 2.2 at the time of color development and a lightness value of 8.9 at the time of color erasure, and having a thickness of about 40 μm, which is reversibly reversible to color by heat and to the color of the fluorescent yellow pigment. It is a thermochromic layer.
The metallic color metallic luster layer 3 has a surface of natural mica of 45
Coated with 4% by weight of titanium oxide, and further coated with 4% by weight of iron oxide, having an optical thickness of 270 nm and a particle size of 10 to 10.
This is a layer having a thickness of about 40 μm and composed of a 50 μm metallic red metallic luster pigment and an acrylate resin.
At 15 ° C. or lower, when the thermochromic layer develops a color and reflects light 5 of 650 to 700 nm, which is a part of incident light, and absorbs light 6 of other wavelengths, the laminate 1 has a metallic reddish color. When the thermochromic layer was decolored at 30 ° C. or higher, the metallic reddish purple metallic luster disappeared, and the color became fluorescent yellow pigment. Reference numeral 9 denotes yellow light reflected by the thermochromic layer 7.

Example 12 In the laminate 1 shown in FIG. 2, the thermochromic layer 7 was formed from a compatible solution of 3-part 2-anilino-3-methyl-6-dibutylaminofluorane, 6 parts bisphenol A, and 50 parts 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 fluorescent green pigment and an acrylate resin The mixed system has a lightness value of 2.3 when the color is developed, and a lightness value of 8.0 when the color is erased, and is reversibly reversible to color by heat and a color of a fluorescent green pigment having a thickness of about 40 μm and a color of a fluorescent green pigment. The metallic color gloss layer 3 was the same as that of Example 2. In the laminate 1, at 15 ° C. or lower, the thermochromic layer develops color, and 380 to 430 nm, which is a part of incident light.
When light 5 is reflected and light 6 of other wavelengths is absorbed,
When the thermochromic layer was decolored at 30 ° C. or higher, the metallic purple color disappeared, and the color became a fluorescent green pigment. Reference numeral 9 denotes pastel blue light reflected by the thermochromic layer 7.

Example 13 In the laminate 1 shown in FIG. 2, the thermochromic layer 7 was made of a compatible solution 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 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 red pigment and an acrylate resin Of a mixed system having a lightness value of 2.4 at the time of color development and a lightness value of 4.8 at the time of color erasing, which is reversibly reversible to color by heat of about 40 μm thick and to the color of the fluorescent red pigment. It is a thermochromic layer. The metallic color metallic luster layer 3 was the same as in Example 3. At a temperature of 15 ° C. or less, the thermochromic layer develops a color and the light 5 of 430 to 500 nm, which is a part of the incident light,
Is reflected and absorbs light 6 of other wavelengths, it becomes a metallic blue metallic glossy color. When the thermochromic layer is decolored at 30 ° C. or more, the metallic blue metallic glossy color disappears and the color of the fluorescent red pigment It became. Reference numeral 9 denotes red light reflected by the thermochromic layer 7.

Example 14 In the laminate 1 of FIG. 2, the thermochromic layer 7 was made of a compatible solution of 3-part 2-anilino-3-methyl-6-dibutylaminofluorane, 6 parts bisphenol A, and 50 parts 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 fluorescent pink pigment, a blue pigment, and an acrylic The mixed system composed of an acid ester resin and a mixed color of a fluorescent pink pigment and a blue pigment has a lightness value of 2.3 when the color value is developed and a lightness value of 5.5 when the color is erased. This is a thermochromic layer for reversibly erasing to a certain lavender color, and the metallic color metallic luster layer 3 was the same as in Example 4.
When the thermochromic layer develops color at 15 ° C. or lower and reflects light 5 of 500 to 540 nm, which is a part of incident light, and absorbs light 6 of other wavelengths, the laminate 1 has a metallic green color. When the thermochromic layer was decolored at 30 ° C. or higher, the metallic green color disappeared, and the color became a lavender color which was a mixed color of a fluorescent pink pigment and a blue pigment. Reference numeral 9 denotes a lavender color light reflected by the thermochromic layer 7.

Example 15 FIG. 3 shows an example of the present invention, in which 2 and 3 are the same layers as in Example 5, except that a thermochromic layer 2 is followed by a non-thermochromic colorant. This is a thermochromic laminate composed of three layers in which a colored layer 8 as a third layer is arranged. The coloring layer 8 is a fluorescent yellow layer having a thickness of about 10 μm and comprising a fluorescent yellow pigment having a lightness value of 8.9 and an acrylate resin. Fifteen
The thermochromic layer develops a color at a temperature of not more than 65 ° C.
When light 5 having a wavelength of 0 to 700 nm is reflected and light 6 having other wavelengths is absorbed, a metallic red metallic luster color is obtained. When the thermochromic layer is decolored at 30 ° C. or more, a metallic red metallic luster color is obtained. Disappeared and became the color of the fluorescent yellow pigment in the lower layer. Reference numeral 10 denotes yellow light reflected by the non-thermochromic coloring layer 8.

Example 16 The metallic luster pigment layer 3 was the same as in Example 2, and the thermochromic layer 2 had a brightness value of 2.2 at the time of color development and a brightness value of 9.0 at the time of color erasure of 2-anilino-color. A thermochromic composition comprising a solution of 3 parts of 3-methyl-6-dibutylaminofluorane, 6 parts of bisphenol A, 25 parts of myristyl alcohol, and 25 parts of cetyl caprate was subjected to an interfacial polymerization method of an epoxy resin / amine-based curing agent. Average particle size 8μ obtained by microencapsulation
m, a second layer having a thickness of about 40 μm and comprising a thermochromic material in the form of microcapsules and an acrylate resin, and the coloring layer 8 is made of a fluorescent orange pigment having a brightness value of 6.3 and an acrylate resin. A fluorescent orange layer having a thickness of about 10 μm. When the thermochromic layer develops color at 20 ° C. or lower, it reflects light 5 having a wavelength of 380 to 430 nm, which is a part of the incident light, and absorbs light 6 having other wavelengths, resulting in a metallic purple metallic luster color. When the thermochromic layer was decolored at 20 ° C. or higher, the metallic purple metallic luster color disappeared, and the color of the fluorescent orange pigment in the lower layer was changed. Reference numeral 10 denotes orange light reflected by the non-thermochromic coloring layer 8.

Example 17 The procedure was the same as that of Example 16 except that the thermochromic material of Example 5 was used instead of the thermochromic material of Example 16 and the thermochromic material was encapsulated in microcapsules. Similarly, the thermochromic layer develops color at 15 ° C. or lower, and 380 to 430 n, which is a part of the incident light.
When light 5 having a wavelength of m is reflected and light 6 having other wavelengths is absorbed, a metallic gloss color of metallic magenta color is obtained,
When the thermochromic layer decolorized at 30 ° C. or higher, the metallic magenta metallic luster color disappeared, and the color of the fluorescent orange pigment in the lower layer was obtained. Reference numeral 10 denotes orange light reflected by the non-thermochromic coloring layer 8.

Example 18 The metallic luster pigment used in Example 3 was used in place of the metallic luster pigment 3 of Example 16, and the coloring layer 8 was replaced with a fluorescent orange pigment and had a brightness of 5.5. Example 16 was the same as Example 16 except that a pink pigment was used. 20 ° C
In the following, the thermochromic layer develops color and 430 which is a part of the incident light
When light 5 having a wavelength of about 500 nm is reflected and light 6 having other wavelengths is absorbed, a metallic blue metallic luster color is obtained. When the thermochromic layer is decolored at 20 ° C. or more, the metallic blue metallic luster color becomes It disappeared and became the color of the fluorescent pink pigment in the lower layer. Reference numeral 10 denotes pink light reflected by the non-thermochromic coloring layer 8.

Example 19 The same procedure as in Example 18 was carried out except that in the colored layer 8 of Example 18, a fluorescent yellow pigment having a lightness value of 8.4 was used instead of the fluorescent pink pigment. Similarly, when the thermochromic layer develops a color at 20 ° C. or lower and reflects light 5 having a wavelength of 430 to 500 nm, which is a part of incident light, and absorbs light 6 having other wavelengths, the metallic luster of metallic blue color is obtained. When the thermochromic layer was decolored at 20 ° C. or higher, the metallic blue metallic luster color disappeared, and the color of the fluorescent yellow pigment in the lower layer was obtained. Reference numeral 10 denotes yellow light reflected by the non-thermochromic coloring layer 8.

Example 20 The metallic luster pigment 3 used in Example 16 was used instead of the metallic luster pigment 3 of Example 16, and the color layer 8 had a brightness value of 4.7 instead of the fluorescent orange pigment. Example 16 was the same as Example 16 except that a fluorescent red pigment was used. Similarly 20
The thermochromic layer develops a color below 50 ° C. and is a part of the incident light.
When the light 5 having a wavelength of 0 to 540 nm is reflected and the light 6 having other wavelengths is absorbed, a metallic green metallic luster color is obtained. When the thermochromic layer is decolored at 20 ° C. or more, the metallic green metallic luster color disappears. , The color of the fluorescent red pigment in the lower layer. Reference numeral 10 denotes red light reflected by the non-thermochromic coloring layer 8.

Example 21 The same procedure as in Example 20 was carried out except that in the colored layer 8 of Example 20, a blue pigment having a lightness value of 5.0 and a white pigment were used instead of the fluorescent red pigment. Similarly, the thermochromic layer develops color at a temperature of 20 ° C. or lower, and 500 to 540 which is a part of incident light.
When light 5 having a wavelength of nm is reflected and light 6 having other wavelengths is absorbed, a metallic green metallic luster color is obtained,
When the thermochromic layer was decolored at 20 ° C. or higher, the metallic green metallic luster color disappeared, and the paste became a pastel blue color which was a mixed color of a blue pigment and a white pigment in the lower layer. Reference numeral 10 denotes pastel blue light reflected by the non-thermochromic coloring layer 8.

Comparative Example 1 In place of the thermochromic material of Example 3, the lightness value at the time of color development was 3.
5. At the time of heat-discoloring decoloring consisting of a compatible solution of 6 parts of 2-anilino-3-methyl-6-dibutylaminofluorane having a lightness value of 6.0 upon decoloration, 10 parts of bisphenol A, and 25 parts of neopentyl stearate. Example 1 was repeated except that the thermochromic composition, which did not become colorless, was used in the form of microcapsules in the form of microcapsules having an average particle diameter of 8 μm, which was obtained by microencapsulation by interfacial polymerization of an epoxy / amine curing agent. Identical. At 15 ° C. or lower, the thermochromic layer develops a color, reflects light 5 having a wavelength of 490 to 500 nm, which is a part of incident light, and absorbs light 6 having other wavelengths. Become. 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 only the metallic blue color is reduced, and the metallic gloss color of the metallic blue color is still low. It does not change reversibly metallic blue color ← → colorless.

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-dibutylaminofluorane, 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 at the time of decoloration of 3.3. The metallic color metallic luster layer 3 was the same as in Example 9. 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 metallic red color is slightly changed to a bluish metallic red color. Appears as a glossy color and does not reversibly change from metallic red to blue.

Comparative Example 3 In place of the fluorescent orange pigment of Example 16, a red pigment was used.
Example 16 was the same as Example 16 except that the red pigment layer of the coloring layer 8 having a brightness value of 3.7 was used. Similarly, the thermochromic layer develops color at a temperature of 20 ° C. or lower, and 380 to 430 which are a part of the incident light.
When light 5 having a wavelength of nm is reflected and light 6 having other wavelengths is absorbed, a metallic gloss color of metallic purple color is obtained.
In this comparative example, even if the thermochromic layer decolorizes at 20 ° C. or more,
Since the transmitted light 6 can still be sufficiently absorbed, the metallic purple color is slightly reddish, and the metallic purple color appears as before, and the metallic purple color reversibly changes from red to red. Absent.

[0059]

Effect of the Invention The thermochromic laminate of the present invention reversibly changes from a metallic metallic luster color to a colorless or non-thermochromic colorant used in combination with a temperature change . 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 thermochromic laminate of a metallic color 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]

 DESCRIPTION OF SYMBOLS 1 Metallic metallic luster thermochromic laminate 2 Thermochromic layer 3 Metallic metallic luster layer 4 Incident light 5 Reflected light 6 Transmitted light 7 Thermochromic layer containing non-thermochromic coloring agent 8 Non-thermochromic coloring layer 9 Light reflected by the thermochromic layer at the time of decoloring 10 Light reflected by the non-thermochromic layer 8 at the time of decoloring

──────────────────────────────────────────────────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 (23)

(57) [Claims] 1. A. First Embodiment 45-58% by weight of natural mica surface
The optical thickness of the coating layer coated with titanium oxide of
A. a layer for adjusting the wavelength of reflected light, which is composed of a metallic metallic luster pigment having a particle size of 415 nm and a particle size of 5 to 60 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 which reversibly changes from a metallic metallic gloss to a colorless color, 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 5 to 58% by weight of titanium oxide has an optical thickness of 245 to 415 nm and a particle size of 5 to 60 μm.
A metallic metallic glossy colored coating layer formed by coating a coating composition comprising a metallic metallic luster pigment, a film-forming material, and a coloring agent;
An optical thickness of a coating layer coated with 8% by weight of titanium oxide having an optical thickness of 245 to 415 nm and a particle size of 5 to 60 μm; B. a layer for adjusting the wavelength of the selected reflected 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 layer selected from a material and a synthetic resin, the thermochromic sheet being a layer selected from the group consisting of a thermochromic sheet 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 metallic 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 metallic metallic 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 is between the lightness value (V4) of the thermochromic material at the time of color development (V4). V3)
A thermochromic laminate in which a non-thermochromic dye / pigment coloring layer is provided, wherein the relation of (V4)> 1 is satisfied, and the color change from a metallic glossy metallic color to a dye / pigment color reversibly. 5. A coating in which a metallic metallic luster pigment coats the surface of natural mica with 45 to 58% by weight of titanium oxide, and further covers it with 0.5 to 10% by weight of a non-thermochromic colored dye. 5. A metallic luster pigment having a layer thickness of 245 to 415 nm and a particle size of 5 to 60 .mu.m. A thermochromic laminate that changes color to a color-changing dye / pigment. 6. A metallic luster pigment of natural red mica having an optical thickness of 245 to 275 nm, wherein the surface of natural mica is coated with 45 to 47% by weight of titanium oxide. 5. A thermochromic laminate which reversibly heat-discolors from a metallic red metallic luster color to a colorless or non-thermochromic dye / pigment described in any one of 5. 7. The metallic luster pigment of claim 1, wherein the metallic luster pigment is a metallic mica pigment having an optical thickness of 280 to 310 nm, wherein the surface of natural mica is coated with 48 to 50% by weight of titanium oxide. 5. A thermochromic laminate which reversibly heat-discolors from a metallic purple metallic luster color to a colorless or non-thermochromic dyestuff pigment according to any one of the above items 5. 8. The metallic luster pigment of claim 1, wherein said metallic luster pigment is a metallic blue pigment having an optical thickness of 315 to 350 nm, wherein the surface of natural mica is coated with 51 to 54% by weight of titanium oxide. 5. A thermochromic laminate which reversibly heat-discolors from a metallic blue metallic luster color to a colorless or non-thermochromic dye / pigment described in any one of 5. 9. The metallic luster pigment of claim 1, wherein said metallic luster pigment is a metallic mica pigment having an optical thickness of 375-415 nm, wherein the surface of natural mica is coated with 55-58% by weight of titanium oxide. A thermochromic laminate which reversibly heat-discolors from a metallic green metallic luster color to a colorless or non-thermochromic dye / pigment described in any one of the above. 10. An organic material in which a thermochromic material reversibly causes a color reaction between an electron-donating compound and an electron-accepting compound.
The thermochromic laminate according to any one of claims 1 to 9, which is a thermochromic material in which the compound medium is encapsulated in microcapsules, the thermochromic laminate reversibly changing from a metallic color to a colorless or dye-pigment color. 11. A coating layer comprising a metallic metallic luster pigment coated on the surface of natural mica with 45 to 58% by weight of titanium oxide and further coated with 4 to 10% by weight of iron oxide has an optical thickness of 245 to 245. The thermochromic laminate which reversibly changes from a metallic metallic luster color to a light yellow color according to any one of claims 1 to 10, which is a metallic metallic luster pigment having a particle size of 415 nm and a particle size of 5 to 60 µm. body. 12. The thermochromic laminate according to claim 1, which is reversibly changed from a metallic metallic luster color to a colorless or dye pigment color, is cut and powdered. Thermochromic granules. 13. The thermochromic laminate according to any one of claims 1 to 10, which reversibly changes from a metallic metallic luster color to a colorless or dye pigment color, is cut into a thread shape. Thermochromic yarn. 14. A. The optical thickness of the coating layer obtained by coating the surface of natural mica with 45 to 58% by weight of titanium oxide is 245.
B. a coating composition comprising a metallic metallic luster pigment having a particle size of 5 to 60 μm, a particle size of 5 to 60 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. thermochromic material and a film-forming material exhibition colorant and is
Two types of coating compositions of the paint sets Narubutsu consisting of a combination, reversibly thermochromic laminate forming two-combination coating material discolored colorless from metallic color of metallic luster color. 15. 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. The thermochromic composition according to claim 14, wherein the mixed color value at the time of decoloring is 6 or less, and the color value (V2) of the mixed system is 4 or more and (V2)-(V1)> 1. A two-component combination coating material for forming a thermochromic laminate, which gradually changes from a metallic metallic luster color to a dye pigment color. 16. A. The optical thickness of the coating layer obtained by coating the surface of natural mica with 45 to 58% by weight of titanium oxide is 245.
B. a coating composition comprising a metallic metallic luster pigment having a particle size of 5 to 60 μm, a particle size of 5 to 60 μm, a coating film forming material and a vehicle; (A) a colorless lightness value of a colorless state in a color-developed state of 6 or less, in which a color reaction between the electron-donating compound and the electron-accepting compound is reversibly induced to form a color formed of an organic compound medium; 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. When a non-thermochromic colored dye or pigment is blended with a thermochromic material having a colorless lightness value of 6 or less and a decolorized colorless lightness value of 8 or more composed of a compound medium and a colorless state. A coating composition wherein the lightness value (V1) of the color density of the mixed system is 6 or less and the lightness value (V2) of the mixed system at the time of decoloring is 4 or more and (V2)-(V1)>1; A thermochromic composition selected from C.I. 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 relationship of-(V4)> 1 is satisfied; A three-component combination coating material for forming a thermochromic laminate that changes color to the color of a pigment. 17. A thermochromic material comprising an electron-donating compound and an electron-accepting compound, and an organic compound which reversibly causes a color reaction between the two.
17. A thermochromic material enclosing a compound medium in microcapsules, according to any one of claims 14 to 16,
Combination coating for forming thermochromic laminates that reversibly changes color from metallic to colorless or pale yellow or dye pigment
Wood . 18. A coating layer in which the surface of natural mica is coated with 45 to 58% by weight of titanium oxide and then coated with 4 to 10% by weight of iron oxide has an optical thickness of 245 to 85%. Metallic luster pigment of 415 nm and particle size of 5 to 60 μm or natural mica
~ 58% by weight of titanium oxide, on which 0.5%
The coating layer coated with a non-thermochromic coloring dye of 10 to 10% by weight has an optical thickness of 245 to 415 nm and a particle size of 5
The thermochromic laminate according to any one of claims 14 to 17, wherein the thermochromic laminate reversibly changes from a metallic metallic luster color to a pale yellow color or a dye / pigment, which is a metallic luster pigment having a metallic color of ~ 60 µm. Combined coating material for body formation. 19. A. The optical thickness of the coating layer obtained by coating the surface of natural mica with 45 to 58% by weight of titanium oxide is 245.
B. a metallic luster coloring sheet formed of a metallic luster pigment having a particle size of 5 μm to 60 μm and a synthetic resin having a particle size of 5 μm to 60 μm; 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-forming sheet that reversibly changes color from a metallic metallic luster color to colorless by combining two types of thermochromic material and a thermochromic sheet molded with a synthetic resin. 20. When the thermochromic sheet contains a thermochromic material and a non-thermochromic colored dye or pigment, 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 is 4 or more and (V2) −
(V1) The thermochromic sheet according to claim 19, which is a thermochromic sheet that reversibly changes from a metallic metallic glossy color to a dye pigment color. 21. A. The optical thickness of the coating layer obtained by coating the surface of natural mica with 45 to 58% by weight of titanium oxide is 245.
B. a metallic luster coloring sheet formed of a metallic luster pigment having a particle size of 5 μm to 60 μm and a synthetic resin having a particle size of 5 μm to 60 μm; (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. And (b) a color density in a color-developed state comprising: a sheet formed from a thermochromic material having a molecular weight of 8 or more; and (b) an organic compound medium that reversibly causes a color reaction between the electron-donating compound and the electron-accepting compound. The lightness value of the color density of a mixed system in which a non-thermochromic colored dye or pigment is blended in addition to a thermochromic material having a lightness value of 6 or less and a colorless lightness value in a decolored state of 8 or more, (V1) is 6 or less, the color value (V2) of the mixed system at the time of decoloring is 4 or more, and (V2)-(V1)>
C. 1 sheet, a thermochromic sheet selected from: The lightness value (V3) of the color density in which a non-thermochromic colored dye or pigment is blended is 4 or more, and between the lightness value (V4) of the thermochromic material at the time of color development, and (V3)-(V4). A three-type sheet for forming a thermochromic laminate, which reversibly changes from a metallic glossy color of a metallic color to a color of a dye / pigment, in which the three types of sheets satisfy the relationship of> 1. 22. A thermochromic material comprising an electron-donating compound and an electron-accepting compound, and an organic compound which reversibly causes a color reaction between the two.
17. A thermochromic material enclosing a compound medium in microcapsules, according to any one of claims 14 to 16,
A combination sheet for forming a thermochromic laminate, which reversibly changes from a metallic color to a colorless or pale yellow color or a color of a dye or pigment. 23. A coating layer in which the surface of natural mica is coated with 45 to 58% by weight of titanium oxide and further coated with 4 to 10% by weight of iron oxide has an optical thickness of 245 to 45%. Metallic luster pigment of 415 nm and particle size of 5 to 60 μm or natural mica
~ 58% by weight of titanium oxide, on which 0.5%
The coating layer coated with a non-thermochromic coloring dye of 10 to 10% by weight has an optical thickness of 245 to 415 nm and a particle size of 5
23. The thermochromic laminate according to any one of claims 19 to 22, which is a metallic luster pigment having a metallic color of ~ 60 m, reversibly changing from a metallic luster color of a metallic color to a pale yellow color or a dye pigment color. Sheet for body formation.