JP3245797B2 - Thermochromic coating film that changes color from a metallic metallic gloss color to a thermochromic color, and a coating composition used to produce the coating film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metallic luster thermochromic coating film of metallic color and a coating composition used to form the coating film. More particularly, the present invention relates to a thermochromic coating film having a metallic luster and exhibiting a reversible color change from a metallic color to a colorless or other color with a change in temperature, and a coating composition used for forming the coating film.

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

However, liquid crystals are inherently colorless and reflect a specific wavelength, which is the selective scattering of visible light. Therefore, a blackish opaque layer is required on the back surface.
Since the color looks black-red-yellow-green-blue-purple-black, the color change does not become clear even if a pearlescent layer is provided thereon.
For example, when a metallic pearlescent pigment is used, the color change is represented by a metallic color-a red with a metallic color-
Metallic yellow-metallic green-metallic blue-metallic purple-metallic, with no clear change to a non-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. However, the metallic color is a gorgeous color, and the discoloration from the metallic color to another color attracts the eyes of the viewer, and there is a strong demand for such a discoloration.

[0004]

SUMMARY OF THE INVENTION The present inventors have conducted research to achieve a vivid and versatile thermal discoloration from a metallic metallic luster color by a thermochromic material, and have completed the present invention. The thermochromic material used in the present invention, unlike liquid crystal, has a distinct 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. There is. Therefore, for example, by using a black-white thermochromic material, it is possible to exhibit a color change from black to white, and by mixing a metallic metallic luster pigment with the thermochromic material, a metallic metallic luster color is obtained. Can make the viewer see the color change of white. Further, a clear color change from a metallic metallic gloss to a colored one by mixing a non-thermochromic colorant can be visually recognized. Further, the lower non-thermochromic coloring layer can be hidden by a metallic glossy coating film. 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. This has the effect that the state can be maintained and 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]

According to the present invention, there is provided a composition comprising: "A. Natural optical mica having a surface coated with 45 to 58% by weight of titanium oxide having an optical thickness of 245 to 415;
B. a metallic metallic luster pigment having a particle size of 5 to 60 μm, 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 material having a value of 8 or more; A transparent paint film-forming material comprising a mixture of a metallic luster pigment of A and a thermochromic material of B in a weight ratio of A: B = 0.25 to 98: 1 and a paint film-forming material A thermochromic coating film that reversibly changes color from metallic metallic luster to colorless. 2. Metallic metallic luster pigment on natural mica surface
Coated with 5 to 58% by weight of titanium oxide and 4 to 10
The optical thickness of the coating layer coated with wt.
2. The thermochromic coating film according to claim 1, which is a metallic luster pigment having a particle size of from 5 to 415 nm and a particle size of from 5 to 60 [mu] m. 3. Further, D. The mixed system containing a non-thermochromic dye / pigment has a color density lightness value (V1) of 6 or less at the time of color development, and the mixed system has a color lightness value (V2) of 4 or more at the time of decoloration (V2)
-The thermochromic coating film according to item 1 or 2, wherein (V1)> 1, reversibly changing from a metallic metallic luster color to a color of a dye or pigment. 4. 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.
4. A thermochromic coating film which reversibly changes the color of a metallic luster from a metallic luster color to a non-thermochromic dye / pigment as described in item 1, which is a metallic luster pigment of μm. 5. Item 1. The metallic luster pigment of metallic color is a metallic luster pigment of metallic red color 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. The thermochromic coating film reversibly heat-discolored from a metallic red metallic luster color to a colorless or non-thermochromic dye / pigment described in any one of the above. 6. 1. The metallic luster pigment of metallic color is a metallic luster pigment of metallic purple color 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. A thermochromic coating film reversibly thermally discolored from a metallic purple metallic luster color to a colorless or non-thermochromic dye described in any one of claims 1 to 4. 7. Item 1. The metallic luster pigment of metallic color is a metallic luster pigment of metallic blue color having an optical thickness of 315 to 350 nm obtained by coating the surface of natural mica with 51 to 54% by weight of titanium oxide. A thermochromic coating film which reversibly heat-discolors from a metallic blue metallic luster color to a colorless or non-thermochromic dye or pigment according to any one of the preceding claims. 8. Any one of the above items 1, 3 and 4, wherein the metallic metallic luster pigment is a metallic green metallic luster pigment having an optical thickness of 375 to 415 nm obtained by coating the surface of natural mica with 55 to 58% by weight of titanium oxide. 4. A thermochromic coating film which reversibly heat-discolors from a metallic green metallic luster color to a colorless or non-thermochromic dye / pigment described in 1 above. 9. 9. The thermochromic material according to any one of items 1 to 8, wherein the thermochromic material is a thermochromic material in which the organic compound medium that reversibly causes a color reaction between the electron-donating compound and the electron-accepting compound and both is encapsulated in microcapsules. The described thermochromic coating film which reversibly changes from a metallic color to a colorless or dye / pigment color. 10. 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 luster pigment having a particle size of 5 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. C. a thermochromic material; A metallic luster pigment of A and a thermochromic material of B are composed of a transparent coating film forming material and a coloring agent, and A: B = 0.25 to 98:
A thermochromic coating composition which is reversibly changed from a metallic metallic color to a colorless compounded in a weight ratio of 1. 11. Item 10. Lightness value of color density of a mixed system in which a non-thermochromic dye / pigment is blended with a coating composition comprising a metallic metallic luster pigment, a thermochromic material, a film-forming material, and a coloring agent described in Item 10 (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)> 1.
A thermochromic coating composition which reversibly changes from a metallic metallic gloss color to a dye pigment color. 12. A metallic metallic luster pigment coats the surface of the natural mica with 45-58% by weight of titanium oxide, on which 0.1% is applied.
The coating layer coated with 5 to 10% by weight of the non-thermochromic coloring dye has an optical thickness of 245 to 415 nm and a particle size of 5 to 6
11. A thermochromic coating composition which reversibly changes from a metallic metallic gloss color to a non-thermochromic dye color as described in item 10 or 11, which is a metallic luster pigment of 0 μm. 13. Metallic metallic luster pigment coats the surface of natural mica with 45-58% by weight of titanium oxide,
The optical thickness of the coating layer coated with 10% by weight of iron oxide is 2
A thermochromic coating which reversibly changes from a metallic metallic luster color to a pale yellow or dye pigment color according to claim 10 or 11, which is a metallic luster pigment having a particle size of 45 to 415 nm and a particle size of 5 to 60 µm. Composition. 14． The thermochromic material is a thermochromic material obtained by encapsulating a microcapsule with an electron-donating compound and an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between the electron-donating compound and the electron-accepting compound.
Item 14. The thermochromic coating composition according to any one of Items 13 to 13, which reversibly changes from a metallic color to a colorless or pale yellow color or a color of a dye or pigment. 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.
In addition, a dichroic metallic luster pigment obtained by coating a metallic metallic luster pigment coated with titanium oxide with a non-thermochromic colored dye pigment is also used. Depending on the weight of the titanium oxide coating and the optical thickness of the coating, the mica coated with titanium oxide separates visible light of red to purple into light of each wavelength and reflects only light of a specific wavelength. It has the function of transmitting 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 pigment is absorbed by the thermochromic material. In this way, the metallic luster light of a specific wavelength is reflected, so that the metallic color becomes a specific color.

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, the surface of natural mica was coated with 45 to 58% by weight of titanium oxide, and the coating layer was further coated with 4 to 10% by weight of iron oxide. Those having a size of 60 μm are also used. The pigment coated with non-thermochromic colored pigment on titanium oxide looks metallic due to wavelength-selective reflection / transmission, and the pigment is coated in an amount that does not affect the metallic color. Accordingly, dichroism of a metallic color and a color of a colored pigment can be exhibited. When the covering ratio of titanium oxide is less than 48% by weight, a sufficient metallic color is hardly produced. On the other hand, if the coverage of titanium oxide exceeds 58% by weight, wavelength selectivity is lost, and the titanium oxide does not look metallic. If the coverage of the colored pigment is less than 0.5% by weight, a sufficient color density of the colored pigment cannot be obtained. If it exceeds 10% by weight, the color density of the color is too high, and the metallic color does not become a dichroic color. When the amount of each pigment is within the above range, it is possible to selectively transmit light having a wavelength of a metallic color and reflect light having a wavelength which is complementary to the metallic color.
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.

[0008] 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 a non-thermochromic coloring dye, the color of the non-thermochromic coloring pigment depends on the color of the coating. , Can express a wide variety of color changes, for example, in combination with black ← → white thermochromic layer, metallic color ← → pink, metallic color ← → blue, etc. metallic color ← → colored Can be visually recognized. The same applies to a metallic pigment in which natural mica is coated with titanium oxide, iron oxide is coated thereon, and a non-thermochromic dye is further coated thereon, except that the light yellow effect of iron oxide is added.

[0009] 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 550-600 nm red-violet light. Most preferably, the thermochromic material is used by being encapsulated in microcapsules. This is because the thermochromic materials are maintained at the same composition under various use conditions and can exhibit the same effects. The thermochromic coating film of the present invention is composed of the above-described metallic luster pigment of a metallic color, a thermochromic material, and a coating film forming material.

The lightness values of the thermochromic material at the time of color development and decoloration are as follows. In an achromatic array, complete black is assumed to be 0, complete white is assumed to be 10, and the difference in the sense of brightness is evenly spaced between them. The lightness value of the Munsell color chart system divided as described above is shown, and the lightness of the chromatic color indicates the lightness value of the achromatic color in which the sensation of the brightness of the chromatic color is equal to this. That is, the smaller the lightness value, the closer to black, and the larger the lightness value, the closer to white, it can be used as an index of how much visible light is absorbed and how much it is reflected. This indicates how visible light transmitted through the metallic luster pigment is reflected and absorbed by the thermochromic material.

[0011]

The heat-modified coating film of the present invention allows the color change of the thermochromic material to be visually recognized through a metallic metallic luster pigment. As described above, the mica coated with titanium oxide is red to red depending on the coating weight of the titanium oxide and the optical thickness of the coating.
It has the function of dispersing violet visible light into light of each color wavelength, reflecting only light of a specific wavelength, 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. The light transmitted through the metallic pigment is absorbed by the thermochromic material. 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, titanium oxide-coated mica whose optical thickness is adjusted to selectively reflect light of a specific color and transmit light of another color, the transmitted light is absorbed by a black thermochromic material, and Since only the color light is reflected, a specific metallic color is exhibited. On the other hand, when the thermochromic material is white, it reflects transmitted light, reflects not only metallic color light but also other color lights, and reflects all visible light wavelengths. Therefore, by changing the thermochromic material reversibly from black to white, the viewer can visually recognize the reversible color change from the specific metallic color to white.

What is important here is that titanium oxide must meet the requirement of an optical thickness of 245 to 415 nm. If the optical thickness of the titanium oxide coated on the natural mica is within the above range, it is reflected in each of red to purple colors corresponding to the thickness, and the reflected light becomes parallel rays due to the action of the mica, so that the metallic luster is reduced. It becomes tinged metallic light.

For example, when the coating weight% of titanium oxide is 45 to 4
7%, pigment with an optical thickness of 245 to 275 nm
Transmits green light of 0 to 550 nm and 650 to 700 n
m red light. When the light transmitted through the metallic pigment is absorbed by the thermochromic material, only the red metallic color is seen by the viewer.

When the thermochromic material reflects the light transmitted through the metallic pigment, the viewer sees all the visible light as it is and looks white because the color of the thermochromic material changes. Expression is 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 55-58%
Pigment having an optical thickness of 375 to 415 nm is 630 to 7
It transmits red light of 00 nm and reflects green light of 500 to 540 nm and has a green metallic color.

The coating weight% 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. The coating weight percentage of titanium oxide is 48 to 50% and the optical thickness is 2
The pigment of 80 to 310 nm transmits yellow light of 530 to 580 nm and reflects violet light of 380 to 430 nm to become a purple metallic color. Thus, the present invention reflects a specific wavelength of light according to the specific titanium oxide coating amount and the optical thickness, and expresses a metallic color by the interference effect of mica and the colorless colorless discoloration effect of the thermochromic material. You can do it.

Further, in a metallic metallic luster pigment in which natural mica particles are coated with titanium oxide on the surface and iron oxide is coated on the titanium oxide particles, in addition to the above-mentioned wavelength-selective reflection and transmission effects, the iron oxide itself has By adding the characteristic of absorbing blue light and reflecting yellow light, a reversible color change from a more vivid metallic color to pale yellow can be made visible. When iron oxide is used in combination, forming an iron oxide film on a titanium oxide film is most effective for developing a metallic metallic luster 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 are mixed, the reflection efficiency of the iron oxide is deteriorated because the titanium oxide may block the reflected light of the iron oxide as compared with the iron oxide being 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 giving depth to color. This is because the reflected light from this layer is not blocked or reflected by other layers due to the presence of the iron oxide film in the upper layer.

As described above, as the thermochromic material, a thermochromic material containing three components of an organic compound medium which reversibly causes a color reaction between the electron donating color compound and the electron accepting compound is used. For example, the following are specifically described in the aforementioned Japanese Patent Publication No. 51-35414. (1) The essential components include (a) an electron-donating color-forming organic compound, (b) a compound having a phenolic hydroxyl group, and (c) a linear aliphatic monohydric alcohol having no polar substituent. Reversible thermochromic material. Or (2) (a) a compound having an electron-donating color-forming organic compound, (b) a compound having a phenolic hydroxyl group, (c) an aliphatic monohydric alcohol having no polar substituent, and having a polar substituent. A reversible thermochromic material comprising, as essential components, three components of a compound selected from an ester having no polar substituent obtained from an aliphatic monocarboxylic acid which is not obtained. Or (3) (a) an electron-donating color-forming organic compound, (b) a compound having a phenolic hydroxyl group, (c) a higher aliphatic monohydric alcohol having no polar substituent, and a polar substituent. The essential component is a compound selected from aliphatic monocarboxylic acids having no polar group and a non-polar substituent-containing ester obtained from a linear aliphatic monohydric alcohol having no polar substituent. And a reversible thermochromic material containing this in a microcapsule. 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. In addition, a thermochromic material containing a color-memorizing thermochromic dye which exhibits a large hysteresis characteristic and is described in JP-A-60-264285, that is, a curve plotting a change in coloring density due to a temperature change Is a type of discoloring material that changes color following a significantly different path depending on whether the temperature rises from a lower temperature side than the discoloration temperature range and conversely, if it is lowered from a higher temperature side than the discoloration temperature range. A thermochromic material having a characteristic of being able to store and retain a state changed at a temperature equal to or lower than the low-temperature side discoloration point or equal to or higher than the high-temperature side discoloration point in a normal temperature range between the low-temperature side discoloration points is also used.

The heat discoloration coating film having metallic metallic luster of the present invention will be specifically described. The heat discoloration coating film of the metallic metallic luster of the present invention comprises (A) a paint film comprising a thermochromic material, a metallic luster pigment of a metallic color and a paint film forming material, and (B) a thermochromic material and a non-discolorable material. A coating film comprising a colorant, a metallic metallic pigment of a metallic color, and a coating film forming material. The discolored coating film may be formed on a support, or a transparent protective film may be provided on the surface. Next, the metallic glossy thermochromic coating film of the metallic color of the present invention will be described based on the above (A) and (B).

In the above coating film (A), the metallic luster pigment is a metallic luster pigment having a particle size of about 5 to 60 μm, and the thermochromic material is an electron-donating color-forming organic compound. A thermochromic material (hereinafter referred to as thermochromic material) comprising a three-component homogeneous solution of an electron-accepting compound and an organic compound medium for reversibly causing a color reaction between the two. The lightness value of the color density in the color-developed state is 6 or less, and the lightness value of the colorless state in the decolored state is 8
It is composed of a thermochromic material and a coating film forming material as described above, and is a metallic metallic glossy thermochromic coating film that exhibits a reversible color change from metallic metallic gloss to colorless, colorless to metallic metallic gloss. is there. In the above, when the brightness value of the color density of the thermochromic material in the color-developing state is 6 or less, the thermochromic material has a capability of sufficiently absorbing light transmitted through the metallic luster pigment of the metallic color. It looks like a metallic metallic luster color clearly. However, when the lightness value of the color development state exceeds 6, the light transmitted through the metallic metallic luster pigment cannot be sufficiently absorbed,
Some also reflect, so that they do not look like a clear metallic metallic luster color. 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 the light is mixed and returns to white light, so that the light looks white. 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 coating film of (B), the metallic luster pigment is a metallic luster pigment having a metallic color of about 5 to 60 μm, and the thermochromic material comprises the thermochromic material and a non-chromogenic colorant. (Dye and pigment) are mixed, the lightness value (V ₁ ) of the color density in the color-developed state is 6 or less, the lightness value (V ₂ ) of the decolored state is 4 or more, and the lightness value (V
₂ ) If the relationship of lightness value (V ₁ )> 1 is satisfied, a metallic metallic gloss heat discoloration exhibiting a reversible color change from metallic metallic gloss to colored, and from colored to metallic metallic gloss. A coating film is formed. In the above, the reason why the lightness value (V ₁ ) of the color density of the mixed color system in the color development state is 6 or less is the same as above. On the other hand, the reason why the color value (V ₂ ) of the mixed color system in the decolored state needs to be 4 or more and the above-mentioned V ₂ −V ₁ > 1 must be satisfied is that in this system, a non-thermochromic dye, Since the pigments are mixed and become colored, 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, blue, 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 or more larger than the lightness value in the color-developed state. 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. However, if it is less than 4, the color density of the mixed color system becomes too deep, and the metallic color is seen even in the decolored state.

The lightness of the thermochromic material at the time of emission and decoloration is smaller, the color is closer to black, and as the lightness is larger, the color is closer to white. It can be used as an index of whether the visible light transmitted through the metallic metallic luster pigment is reflected or absorbed by the thermochromic material. Therefore, if the thermochromic material has a lightness value of 6 or less, it has the ability to sufficiently absorb visible light transmitted through the metallic metallic luster pigment, and as a result, only the yellow light reflected by the metallic metallic luster pigment is emitted. It looks metallic because it is visible. On the other hand, when the lightness value is 8 or more, the visible light transmitted through the metallic metallic luster pigment is reflected. Therefore, the yellow light reflected by the metallic metallic luster pigment and the light reflected by the thermochromic material are reflected. Because both will be seen together, they will not be visible 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 a TC-3600 color difference meter manufactured by Tokyo Denshoku Co., Ltd. 1. Measurement of lightness value of thermochromic material (including a system mixed with non-color-changing dye / pigment) (1) Measurement of lightness value of thermochromic material (color ← → colorless) 10 parts of thermochromic material, 50% Acrylic 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 material (color I ← → color II) 10 parts of thermochromic material, desired amount of non-thermochromic dye, 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.

Next, a coating 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, polystyrene resin, high-impact polystyrene resin, polypropylene resin,
Polymethylstyrene resin, polyacrylate resin, polymethylmethacrylate resin, epoxy resin, epoxyacrylate resin. 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 , Unsaturated polyester resin, polyurethane resin, vinyl acetate emulsion resin, styrene-butadiene emulsion resin, acrylate ester 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. Examples include cellulose acetate, cellulose nitrate, ethyl cellulose, and cellulose derivatives. The thermochromic coating film of the present invention is a coating film formed by applying a coating composition.

Next, the coating composition will be described. The coating film is formed by applying a coating composition on the surface of a substrate. As the substrate, in addition to various films and sheets, the surface of the molded article itself is used. That is, a thermochromic coating film can be formed on the surface of the molded article to obtain a thermochromic molded article. As the base material, paper, synthetic paper, cloth, nonwoven fabric, synthetic leather, leather, plastic, glass, ceramics, metal, wood, stone, and the like are used. In addition, not only a flat shape but also a material having a processed surface such as an uneven shape or a fibrous shape can be used. The coating film is formed by a conventionally known coating film forming method, for example, printing means such as screen printing, offset printing, gravure printing, coater, tampo printing, transfer printing, brush coating, spray coating, electrostatic coating, electrodeposition. The coating can be performed by means such as coating, flow coating, roller coating, dip coating, and the like, or can be formed into a film-sheet by extrusion molding or the like. In addition, an ultraviolet absorber, an infrared absorber, an antioxidant, a singlet oxygen quencher, an antioxidant, an antistatic agent, a polarity imparting agent, a thixotropic agent, an antifoaming agent, a stabilizer, a plasticizer, a flame retardant, Additives such as extenders, lubricants, and foaming agents can be added as necessary to improve the function.

[0025]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will now be described with reference to the drawings. Example 1 FIG. 1 shows an example of the present invention, where 1 is a thermochromic coating film composed of one layer. No. 1 has a natural mica surface coated with 47% by weight of titanium oxide and has an optical thickness of 265 nm and a particle size of 1
0-60 μm metallic red metallic luster pigment and 2-
Microencapsulation of a thermochromic composition comprising a compatibilizer of 3 parts of anilino-3-methyl-6-dibutylaminofluoran, 6 parts of bisphenol A and 50 parts of neopentyl stearate by an interfacial polymerization method of an epoxy resin / amine curing agent In the form of microcapsules having an average particle size of 8 μm obtained in the above, the thickness of a thermochromic material having a lightness value of 2.2 at the time of coloring and a lightness value of 9.0 at the time of decoloring, and an acrylic ester resin A layer that reversibly develops and decolors with heat of 100 μm. The mixing ratio of the metallic red metallic luster pigment and the thermochromic material is 1: 1. In the formulation examples, “parts” means “parts by weight”, and the same applies to the following examples. 15 ℃
In the following, the thermochromic material develops a color, reflects light 3 having a wavelength of 650 to 700 nm, which is a part of the incident light 2, and absorbs light 4 having other wavelengths, resulting in a metallic red metallic luster color. When the thermochromic material loses its color at 30 ° C. and reflects the transmitted light 4 as 5, all the incident light is reflected, and the metallic red metallic gloss color disappears and becomes colorless.

Example 2 The surface of natural mica was coated with 48% by weight of titanium oxide.
A metallic purple metallic luster pigment having an optical thickness of 295 nm and a particle size of 10 to 60 μm, and 2-anilino-3
A thermochromic composition comprising a compatible solution of 3 parts of -methyl-6-dibutylaminofluorane, 6 parts of bisphenol A, and 50 parts of neopentyl stearate is obtained by microencapsulation of an epoxy resin / amine-based curing agent by an interfacial polymerization method. About 100 μm of a thermochromic material and an acrylate resin having a lightness value of 2.2 at the time of coloring and a lightness value of 9.0 at the time of decoloring in the form of microcapsules having an average particle size of 8 μm.
Is a layer that reversibly develops and decolors by the heat of.
The mixing ratio between the metallic purple metallic luster pigment and the thermochromic material is 1: 1. When the thermochromic material develops color at 15 ° C. or less, reflects light having a wavelength of 380 to 430 nm, which is a part of incident light, and absorbs light having other wavelengths,
It becomes a metallic purple metallic luster color, and at 30 ° C. or higher, the thermochromic material is decolorized, and when transmitting light is reflected, all incident light is reflected, and the metallic purple metallic luster color disappears and becomes colorless.

Example 3 The surface of natural mica was coated with 52% by weight of titanium oxide.
A metallic blue metallic luster pigment having an optical thickness of 330 nm and a particle size of 10 to 60 μm, and 2-anilino-3-
A thermochromic composition comprising a compatible solution of 3 parts of methyl-6-dibutylaminofluorane, 6 parts of bisphenol A, and 50 parts of neopentyl stearate was obtained by microencapsulation of an epoxy resin / amine-based curing agent by an interfacial polymerization method. In the form of a microcapsule having an average particle size of 8 μm, the lightness at the time of color development is 2.2, and the lightness at the time of decolorization is 9.0. , A layer that reversibly develops and decolors. still,
The mixing ratio between the metallic blue metallic luster pigment and the thermochromic material is 1: 1. When the thermochromic material develops a color at 15 ° C. or less, reflects light having a wavelength of 430 to 500 nm, which is a part of incident light, and absorbs light having other wavelengths, it becomes a metallic blue metallic luster color, At 30 ° C. or higher, the thermochromic material loses its color and reflects transmitted light, which reflects all incident light, and the metallic blue metallic luster disappears and becomes colorless.

Example 4 The surface of natural mica was coated with 57% by weight of titanium oxide.
A metallic green metallic luster pigment having an optical thickness of 395 nm and a particle size of 10 to 60 μm, and 2-anilino-3
A thermochromic composition comprising a compatible solution of 3 parts of -methyl-6-dibutylaminofluorane, 6 parts of bisphenol A, and 50 parts of neopentyl stearate is obtained by microencapsulation of an epoxy resin / amine-based curing agent by an interfacial polymerization method. About 100 μm of a thermochromic material and an acrylate resin having a lightness value of 2.2 at the time of coloring and a lightness value of 9.0 at the time of decoloring in the form of microcapsules having an average particle size of 8 μm.
Is a layer that reversibly develops and decolors by the heat of.
The mixing ratio between the metallic green metallic luster pigment and the thermochromic material is 1: 1. When the thermochromic material develops color at 15 ° C. or less, reflects light having a wavelength of 500 to 540 nm, which is a part of incident light, and absorbs light having other wavelengths,
It becomes a metallic green metallic luster color, and the thermochromic material is decolorized at 30 ° C. or higher, and if transmitted light is reflected, all incident light is reflected, and the metallic green metallic luster color disappears and becomes colorless.

Example 5 A natural red mica pigment having a surface of natural mica coated with 47% by weight of titanium oxide and having an optical thickness of 265 nm and a particle size of 10 to 60 μm, and a lightness value at the time of color development of a mixed system were obtained. 2.3, 3 parts of 2-anilino-3-methyl-6-dibutylaminofluoran having a lightness value at the time of decoloration of 8.0,
6 parts of bisphenol A, neopentyl stearate 50
Thermochromic material in the form of microcapsules having an average particle size of 8 μm and a fluorescent green pigment obtained by microencapsulation of the thermochromic composition comprising a part of the compatibilizer by an interfacial polymerization method of an epoxy resin / amine-based curing agent, and This layer is made of an acrylic acid ester resin and has a thickness of about 100 μm and reversibly performs color development and decoloration. The mixing ratio of the metallic red metallic luster pigment, the thermochromic material, and the fluorescent green pigment is 1: 1: 0.27. At 15 ° C. or lower, the thermochromic material develops a color and is 650-70 which is a part of the visible light of the incident light.
When light of a wavelength of 0 nm is reflected and light of other wavelengths is absorbed, a metallic red metallic luster color is obtained,
When the thermochromic material loses its color above ℃, the metallic red metallic luster color disappears and it becomes a fluorescent green color.

Example 6 The surface of natural mica was coated with 48% by weight of titanium oxide.
Metallic purple metallic luster pigment having an optical thickness of 295 nm and a particle size of 10 to 60 μm, and a 2-anilino pigment having a lightness value of 2.3 when the mixed system is colored and a lightness value of 8.0 when the color is erased. 3-methyl-6-dibutylaminofluoran 3
Part, bisphenol A 6 parts, neopentyl stearate 50 parts of a thermochromic composition comprising a compatibilized solution of an epoxy resin / amine-based curing agent by an interfacial polymerization method in the form of microcapsules having an average particle size of 8 μm. This layer is made of a thermochromic material, a fluorescent green pigment, and an acrylate resin, and has a thickness of about 100 μm and reversibly performs color development and decoloration. The mixing ratio of the metallic purple metallic luster pigment, the thermochromic material and the fluorescent green pigment is 1: 1: 0.27. At 15 ° C. or lower, the thermochromic material develops a color and is 380 which is a part of visible light of incident light.
Reflecting light having a wavelength of ４430 nm and absorbing light of other wavelengths, it becomes a metallic purple metallic luster color, and when the thermochromic material decolorizes at 30 ° C. or more, the metallic purple metallic luster color disappears, It becomes a fluorescent green color.

Example 7 The surface of natural mica was coated with 52% by weight of titanium oxide.
A metallic blue metallic luster pigment having an optical thickness of 330 nm and a particle size of 10 to 60 μm, and a 2-anilino pigment having a lightness value of 2.2 when the mixed system is colored and a lightness value of 8.9 when the color is erased. 3-methyl-6-dibutylaminofluoran 3
Part, bisphenol A 6 parts, neopentyl stearate 50 parts of a thermochromic composition comprising a compatibilized solution of an epoxy resin / amine-based curing agent by an interfacial polymerization method in the form of microcapsules having an average particle size of 8 μm. This layer is made of a thermochromic material, a fluorescent yellow pigment, and an acrylate resin, and has a thickness of about 100 μm and reversibly performs color development and decoloration. The mixing ratio of the metallic blue metallic luster pigment, the thermochromic material and the fluorescent yellow pigment is 1:
1: 0.3. At 15 ° C. or lower, the thermochromic material develops a color and is 430 to 500 nm which is a part of the visible light of the incident light.
When light of wavelengths other than the above is reflected and light of other wavelengths is absorbed, it becomes a metallic blue metallic glossy color. When the thermochromic material loses color at 30 ° C or higher, the metallic blue metallic glossy color disappears and the fluorescent yellow color The color of the pigment.

Example 8 The surface of natural mica was coated with 57% by weight of titanium oxide.
2-anilino-3 having an optical thickness of 395 nm, a metallic green metallic luster pigment having a particle size of 10 to 60 μm, and a mixed system having a lightness value of 2.7 when coloring and a lightness value of 6.0 when decolorized. -Methyl-6-dibutylaminofluoran 3
Part, bisphenol A 6 parts, neopentyl stearate 50 parts of a thermochromic composition comprising a compatibilized solution of an epoxy resin / amine-based curing agent by an interfacial polymerization method in the form of microcapsules having an average particle size of 8 μm. This layer is made of a thermochromic material, a fluorescent orange pigment, and an acrylate resin and has a thickness of about 100 μm and reversibly performs color development and decoloration by heat. The mixing ratio of the metallic green metallic luster pigment, the thermochromic material and the fluorescent orange pigment is 1: 1: 0.22. At 15 ° C. or lower, the thermochromic material develops a color and is a part of the visible light of incident light, 500
Reflecting light of wavelengths up to 540 nm and absorbing light of other wavelengths results in a metallic green metallic luster color. When the thermochromic material decolorizes above 30 ° C., the metallic green metallic luster color disappears and the fluorescent orange The color of the pigment.

Example 9 The surface of natural mica was coated with 45% by weight of titanium oxide and further coated with 4% by weight of iron oxide to obtain an optical thickness of 270.
Dichroic metallic reddish purple metallic luster pigment, which changes from a metallic reddish purple color with a particle size of 10 to 50 μm in yellow, 3 parts of 2-anilino-3-methyl-6-dibutylaminofluoran, bisphenol A6 Parts, a thermochromic composition comprising a compatibilizer of neopentyl stearate (50 parts) in the form of microcapsules having an average particle size of 8 μm obtained by microencapsulation by an interfacial polymerization method of an epoxy resin / amine-based curing agent. This layer is made of a thermochromic material having a lightness value of 2.2 and a lightness value at the time of decoloration of 9.0 and an acrylic acid ester resin and having a thickness of about 100 μm, and reversibly performs color development and decoloration by heat. . still,
The mixing ratio of the metallic reddish purple metallic luster pigment to the thermochromic material is 1: 1 :. At 15 ° C. or less, the thermochromic material develops a color, and 650 to 7 which is a part of the incident light.
Reflects light with a wavelength of 00 nm and absorbs light of other wavelengths, resulting in a metallic reddish purple metallic luster color. When the thermochromic material decolorizes at 30 ° C or higher, a metallic reddish purple metallic luster color Disappears and turns yellow.

Comparative Example 1 In place of the thermochromic material of Example 1, the lightness value at the time of coloring was 4.0.
5. 2-anilino-3- having a lightness value at the time of decoloration of 6.0.
A non-colorless thermochromic composition comprising a compatible solution of 6 parts of methyl-6-dibutylaminofluorane, 10 parts of bisphenol A and 25 parts of neopentyl stearate is microencapsulated by an interfacial polymerization method of an epoxy resin / amine curing agent. Example 1 is the same as Example 1 except that the obtained thermochromic material in the form of microcapsules having an average particle size of 8 μm is used.
When the thermochromic material develops a color at 15 ° C. or less, reflects light having a wavelength of 650 to 700 nm, which is a part of incident light, and absorbs light having other wavelengths, it becomes a metallic red metallic luster color. . In this comparative example, even if the thermochromic material decolorizes at 30 ° C. or higher, the transmitted light 4 can still be sufficiently absorbed, so that the metallic red color is slightly reduced.
It still looks like a metallic red metallic luster.

Comparative Example 2 The surface of natural mica was coated with 52% by weight of titanium oxide.
A metallic blue metallic luster pigment having an optical thickness of 330 nm and a particle size of 10 to 60 μm, and 2-anilino- having a mixed system having a lightness value of 2.5 when coloring and a lightness value of 3.3 when decolorized. 3-methyl-6-dibutylaminofluoran 6
Parts, 10 parts of bisphenol A and 25 parts of neopentyl stearate in the form of microcapsules having an average particle size of 8 μm obtained by microencapsulation of an epoxy resin / amine-based curing agent by an interfacial polymerization method. This is a layer having a thickness of about 100 μm and comprising a thermochromic material, a red pigment, and an acrylate resin. The mixing ratio of the metallic blue metallic luster pigment, the thermochromic material, and the red pigment is 1: 1: 0.86. At 15 ° C. or lower, the thermochromic material develops a color and 430 to 500 nm which is a part of the incident light.
When light having a wavelength of? Is reflected and light having other wavelengths is absorbed, a metallic blue metallic luster color is obtained. In this comparative example, even if the thermochromic material is decolorized at 30 ° C. or higher, the transmitted light can still be sufficiently absorbed, so that the material has a reddish tint and looks like a metallic blue metallic luster color as before.

[0036]

The thermochromic coating film of the present invention reversibly changes its color from a metallic metallic gloss to a colorless color or a non-thermochromic colorant used in combination with a change in temperature. In the present invention, the function of the thermochromic material used is maintained as it is,
The function can be effectively exhibited. That is, in the discoloration, in a system in which a thermochromic material having an extremely small hysteresis width is applied, the color changes in response to high sensitivity due to a temperature change,
In a system using a thermochromic material having an intermediate hysteresis width, the color changes with a response corresponding to a temperature change. In a system using a thermochromic material with an extremely large hysteresis width,
Even after removing the heat or cold required for the color change, the changed state is maintained in the normal temperature range, and the state can be visually recognized.

[Brief description of the drawings]

FIG. 1 is an explanatory view of a thermochromic coating film of a metallic color which is an example of the present invention.

[Explanation of symbols]

 1 Metallic metallic luster thermochromic coating film 2 Incident light 3 Partial reflected light 4 Incident light 5 Remaining reflected light

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C09D 5/26

Claims (14)

(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
B. a metallic metallic luster pigment having a particle size of 415 nm and a particle size of 5 to 60 μm; 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 material having a value of 8 or more; A transparent paint film-forming material comprising a mixture of a metallic luster pigment of A and a thermochromic material of B in a weight ratio of A: B = 0.25 to 98: 1 and a paint film-forming material A thermochromic coating film that reversibly changes color from metallic metallic luster to colorless. 2. 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 245. The thermochromic coating film according to claim 1, which is a metallic luster pigment having a metallic color of 415 nm and a particle size of 5 to 60 µm. 3. The method according to claim 1, wherein The mixed system containing a non-thermochromic dye / pigment has a color density lightness value (V1) of 6 or less at the time of color development, and the mixed system has a color lightness value (V2) of 4 or more at the time of decoloration (V2) 3. The thermochromic coating film according to claim 1, wherein-(V1)> 1 and reversibly changes from a metallic metallic luster color to a color of a dye or pigment. 4. A coating comprising a metallic metallic luster pigment coated on the surface of natural mica with 45 to 58% by weight of titanium oxide and a further 0.5 to 10% by weight of a non-thermochromic colored dye. 2. A reversibly discolorable metallic luster color to a non-thermochromic dye pigment according to claim 1, wherein the layer is a metallic luster pigment having an optical thickness of 245 to 415 nm and a particle size of 5 to 60 [mu] m. Thermochromic coating film. 5. The metallic luster pigment of claim 1, wherein the metallic luster pigment of natural color 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. 3. A thermochromic coating film which reversibly heat-discolors from a metallic red metallic luster color to a colorless or non-thermochromic dye / pigment described in any one of items 3 and 4. 6. The metallic luster pigment of claim 2, wherein said 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. 3. A thermochromic coating film which reversibly heat-discolors from a metallic purple metallic luster color to a colorless or non-thermochromic dye / pigment described in any one of items 3 and 4. 7. The metallic luster pigment of claim 1, wherein the metallic luster pigment is a natural blue mica pigment having an optical thickness of 315-350 nm, wherein the surface of natural mica is coated with 51-54% by weight of titanium oxide. The thermochromic coating film reversibly heat-discolored from a metallic blue metallic luster color to a colorless or non-thermochromic dye described in any one of items 3 and 4. 8. The metallic luster pigment of claim 1, wherein the metallic luster pigment is a metallic mica 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. 4. The thermochromic coating film reversibly heat-discolored from a metallic green metallic luster color to a colorless or non-thermochromic dye / pigment described in any one of 4. 9. The thermochromic material according to claim 1, wherein the thermochromic material is a thermochromic material encapsulating a microcapsule with an electron-donating compound and an electron-accepting compound, and an organic compound medium for reversibly causing a color reaction between the two. A thermochromic coating film reversibly changing from a metallic color to a colorless or dye / pigment color as described in any one of the above items. 10. 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.
A metallic metallic luster pigment having a particle size of 5 to 60 µm having a particle size of 〜415 nm; A lightness value of a color density of 6 or less and a colorless lightness value of a decolored state of 8 or more composed of an electron-donating compound, an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between the two. C. a thermochromic material; A metallic luster pigment of A and a thermochromic material of B are composed of a transparent coating film forming material and a coloring agent, and A: B = 0.25 to 98:
A thermochromic coating composition which is reversibly changed from a metallic metallic color to a colorless compounded in a weight ratio of 1. 11. A mixed system at the time of color development in which a non-thermochromic dye / pigment is blended with a coating composition comprising the metallic metallic luster pigment of claim 10, a thermochromic material, a film-forming material, and a coloring agent. The lightness value (V1) of the color density 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) A thermochromic coating composition which reversibly changes from a metallic metallic luster color to a dye pigment color, which is a composition of> 1. 12. A coating in which a metallic metallic luster pigment is coated on the surface of natural mica with 45 to 58% by weight of titanium oxide and further coated with 0.5 to 10% by weight of a non-thermochromic colored dye. The reversibly metallic metallic non-thermochromic dye / pigment according to claim 10 or 11, which is a metallic metallic luster pigment having an optical thickness of 245 to 415 nm and a particle size of 5 to 60 µm. A thermochromic coating composition that changes color. 13. 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. A thermochromic coating composition which reversibly changes from a metallic metallic luster color to a pale yellow color or a dye pigment color according to claim 10 or 11, which is a metallic luster pigment having a particle size of 5 to 60 µm and a particle size of 5 to 60 µm. object. 14. The thermochromic material according to claim 10, wherein the thermochromic material is a thermochromic material in which an electron-donating compound and an electron-accepting compound and an organic compound medium for reversibly causing a color reaction between the two are microencapsulated. The thermochromic coating composition according to any one of the preceding claims, which reversibly changes from a metallic color to a colorless or pale yellow color or a color of a dye or pigment.