JPH061068A - Thermal discoloring laminate and composition and sheet used for manufacturing the laminate - Google Patents

Abstract

PURPOSE:To obtain a laminate reversibly changing from silver color to a colorless state by using a layer consisting of a silver metallic gloss pigment and a film forming material and adjusting the wavelength of reflected light as a first layer and employing a layer made of a thermal discoloring material, in which the lightness value of color concentration under the state of color developing and the brightness value of the colorless state under a decolored state have different characteristic values respectively, and the film forming material as a second layer. CONSTITUTION:A layer composed of a silver metallic gloss pigment, in which the optical thickness of a coating layer, in which the surface of natural mica is coated with 16-39wt.% titanium oxide, is 110-170nm and grain size is 5-100mum, and a film forming material and adjusting the wavelength of reflected light is used as a first layer 3. A layer made of a thermal discoloring material, which is made up of an electron donative compound, an electron acceptable compound and an organic compound medium reversibly generating both coloration reactions and in which the lightness value of color concentration under the state of color developing is six or less and the lightness value of a colorless state under a decolored state is eight or more, and the film forming material as a second layer 2. Accordingly, a thermal discoloring laminate thermally discoloring from silver to the colorless state reversibly can be obtained.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Conventionally, thermochromic materials exhibiting a reversible color change of colored ← → colorless and colored [1] ← → colored [2] due to temperature change have been disclosed in JP-B-51-44706 and JP-B-5-7066.
1-444707, JP-B-51-44708, JP-B-52-7764, JP-B-51-465.
No. 48, Japanese Unexamined Patent Publication No. 62-140881, etc., the thermochromic material colored by utilizing this is put to practical use as a temperature indicating element, a toy element, a magic element and the like.

However, a thermochromic material exhibiting a reversible change from a silvery metallic luster color to a colorless color and a reversible color change to another different color due to a temperature change, and a thermochromic material that clearly expresses the color change. Is not yet known. In addition to this, attempts to diversify color changes are made in 3-14400.
It is disclosed in the publication. The thermochromic material described in this publication covers the thermosensitive liquid crystal with a pearlescent layer to try to develop a pearlescent color change.

However, the liquid crystal is essentially colorless and reflects a specific wavelength that is selective scattering of visible light, so that a blackish opaque layer is necessary on the back surface, and therefore the color change is
Since it looks black-red-yellow-green-blue-purple-black, even if a pearlescent layer is provided on it, the color change is not clear.
For example, when a silver pearlescent pigment is used, the color change is silvery-silvered red-silvered yellow-silvered green-silvered blue-silvered purple-silver with a metallic luster. No clear change to no color.
Further, it is not possible to develop a color change from pearlescent color to colorless, and it is impossible to hide or reveal the base.
Since silver is a gorgeous and prominent color, and the change from silver attracts the attention of the viewer, there has been a great demand for a material that makes such a color change.

[0005]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted researches in order to effectively exhibit the color-changing effect of a thermochromic material and change the color of a silver metallic luster color vividly and variably to complete the present invention. It was. Thermochromic material used in the present invention, unlike liquid crystal, because the thermochromic material itself has a clear color change, it is not necessary to provide a blackish opaque layer in the lower layer,
Moreover, it has the feature that it can change from colored to colorless. All visible light appears white when reflected. In this case, when part of the light of all wavelengths of the incident light is absorbed and the rest is reflected, it becomes dark and becomes gray. Since the mica is arranged in layers, the reflected light is not diffusely reflected but reflected in the same direction. Such reflected light has a metallic luster. Therefore, the gray with metallic luster becomes silver. In this way, the silver surface of metallic luster is exposed. It is also possible to make the viewer visually recognize a clear color change from a silver metallic luster color to a color by mixing a non-color-changing colorant. Further, it is possible to have a structure in which the underlying colored layer is made to be concealed with a metallic luster color. This kind of color change and 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, that is, a coloring material containing a so-called color-memory thermosensitive dye, the state changed even after the heat or cold heat required for thermochromic is removed. It can be held and also has the effect of making it visible at room temperature. Since the color change due to heat of the silver metallic luster color is clearly exhibited in this manner, the present invention is widely used in the fields of decoration, interior, toys, stationery, and information.

[0006]

According to the present invention, "1. A. The surface of natural mica is coated with 16 to 39% by weight of titanium oxide, the optical layer has an optical thickness of 110 to 170.
a layer for adjusting the wavelength of reflected light, which is composed of a silver metallic luster pigment having a particle size of 5 to 100 μm and a film forming material, as the first layer, and B. A thermochromic material comprising an electron-donating compound, an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between the both, and a colorless lightness in a decolored state with a lightness value of 6 or less in a colored state. A thermochromic laminate in which a layer formed of a thermochromic material having a value of 8 or more and a film-forming material is used as a second layer to reversibly change from a metallic luster color of silver to colorless. 2. A. The first layer is (a) 16-39 on the surface of natural mica.
The optical thickness of the coating layer coated with 1% by weight of titanium oxide is 1
A silver metallic luster color coating layer formed by coating with a coating composition consisting of a silver metallic luster pigment having a particle size of 5 to 100 μm and a particle size of 5 to 100 μm, a coating film forming material and a color developing agent,
(B) A silver color formed by a synthetic resin and a silver metallic luster pigment having an optical thickness of 110 to 170 nm and a particle size of 5 to 100 μm, in which the surface of natural mica is coated with 16 to 39% by weight of titanium oxide. A metallic luster coloration sheet of, and a layer for adjusting the wavelength of reflected light selected from and B. The second layer is a thermochromic material comprising (a) an electron-donating compound, an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between the two, and the lightness value of the color density in the colored state is 6 or less. A layer formed by coating a coating composition comprising a thermochromic material having a colorless lightness value of 8 or more in a decolored state, a coating film forming material and a color developing agent, and (b) an electron donating compound and an electron accepting property. A thermochromic material comprising a compound and an organic compound medium that reversibly causes a color reaction between the both, and a thermochromic material having a color density of 6 or less in a colored state and a colorless brightness value of 8 or more in a decolored state. A thermochromic laminate that reversibly changes from a silver metallic luster color to colorless, according to item 1, which is a thermochromic layer selected from a material and a thermochromic sheet formed of a synthetic resin. 3. The second thermochromic layer is a thermochromic material in which a non-thermochromic colored dye or pigment is mixed, and the lightness value (V1) of the color density of the mixed system at the time of coloring is 6 or less, and the mixture at the time of decoloring The color lightness value (V2) of the system is 4 or more and (V2)-(V
1) A thermochromic laminate which reversibly changes from a silver metallic luster color to a dye / pigment color according to item 1 or 2, wherein 1 >> 1. 4. The non-thermochromic layer next to the thermochromic layer of the thermochromic laminate according to any one of 1 to 3 which reversibly changes from a silver metallic luster color to a colorless or dye / pigment color. (V3)-(V4) between the lightness value (V4) of the color density formed by the colored dye or pigment and the film-forming material is 4 or more and the lightness value (V4) at the time of color development of the thermochromic material. A thermochromic laminate in which a non-thermochromic dye / pigment coloring layer is arranged and which reversibly changes from a silver metallic luster color to a dye / pigment color. 5. 5. The thermochromic material is a thermochromic material in which an organic medium that reversibly causes a color reaction between an electron-donating compound and an electron-accepting compound is encapsulated in a microcapsule. The thermochromic laminate that reversibly changes from a silver metallic luster color to a colorless or dye-pigmented color. 6. A thermochromic granule obtained by cutting and powdering the thermochromic laminate, which is reversibly discolored from a metallic luster color of silver to colorless or a color of a dye or pigment described in any one of 1 to 5 above. 7. A thermochromic yarn which is formed into a thread by cutting the thermochromic laminate, which is reversibly discolored from the metallic luster color of silver to colorless or to the color of a dye or pigment, according to any one of 1 to 5 above. 8. A. The optical thickness of the coating layer formed by coating the surface of natural mica with 16 to 39% by weight of titanium oxide is 180 to 240 n.
a silver metallic luster pigment having a particle size of 5 to 100 μm, a coating film-forming material, and a colorant, and B. The lightness value of the color density in the colored state is 6 or less and the colorless lightness value in the decolored state is 8 or more, which is composed of an electron-donating compound, an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between them. A thermochromic laminate that reversibly changes from a silver metallic luster color to a colorless color by combining two types of coating compositions, a thermochromic material, a coating composition comprising a film-forming material, and a color-developing agent. Two-component coating composition for body formation. 9. The coating composition consisting of a thermochromic material, a coating film-forming material and a color-developing agent is blended with a non-thermochromic colored dye or pigment and the lightness value (V1) of the color density of the mixed system is 6 or less. The reversibly silvery metallic luster according to item 8, which is a thermochromic composition in which the color value (V2) of the mixed system at the time of decoloring is 4 or more and (V2)-(V1)> 1. A two-component coating composition for forming a thermochromic laminate, which changes color from the color of a dye or pigment. 10. A. The optical thickness of the coating layer formed by coating the surface of natural mica with 16 to 39% by weight of titanium oxide is 110 to 170.
B. a coating composition comprising a silver metallic luster pigment having a particle size of 5 to 100 μm, a coating film forming material and a color developing agent; (A) Colorless lightness value in a decolored state with a lightness value of 6 or less in a coloration state, which is composed of an electron-donating compound, an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between them. Having a value of 8 or more, a coating composition comprising a thermochromic material, a film-forming material and a color-developing agent, and (b) an organic compound that reversibly causes a color reaction between the electron-donating compound and the electron-accepting compound. A thermochromic material having a color density of 6 or less in a color-developed state and a colorless brightness value of 8 or more in a decolorized state, a film-forming material, and a non-thermochromic colored dye comprising a compound medium. Alternatively, the lightness value (V1) of the color density of the mixed system at the time of color development containing a pigment is 6 or less, and the lightness value (V) of the mixed system at the time of decolorization (V
2) is 4 or more and (V2)-(V1)> 1 coating composition, and a thermochromic composition selected from C.I. Between the lightness value (V3) of the color density formed by the non-thermochromic dye or pigment, the coating film forming material and the color developing agent is 4 or more, and the lightness value (V4) at the time of color development of the thermochromic material. To (V
3)-(V4)> 1 is established, and a non-thermochromic dyeing / pigment coloring coating composition, which is a reversible silver metallic luster color in combination with three types of overcoating coating compositions. A three-pack type coating composition for forming a thermochromic laminate that changes its color. 11. 8. The thermochromic material is a thermochromic material in which microcapsules are encapsulated with an electron-donating compound, an electron-accepting compound, and an organic medium that reversibly causes a color reaction between them.
The liquid coating composition for thermochromic shaving formation, which reversibly changes from silver to colorless or to the color of a dye or pigment, according to any one of items. 12. A. The optical thickness of the coating layer formed by coating the surface of natural mica with 16 to 39% by weight of titanium oxide is 110 to 170.
a silver metallic luster coloring sheet formed of a silver metallic luster pigment having a particle size of 5 to 100 μm and a resin, and B. The lightness value of the color density in the colored state is 6 or less and the colorless lightness value in the decolored state is 8 or more, which is composed of an electron-donating compound, an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between them. A sheet for forming a thermochromic laminate, which reversibly changes from a metallic luster color of silver to colorless, which is a combination of two types of sheets, which are a thermochromic material and a thermochromic sheet formed of a resin. 13. The thermochromic sheet contains a non-thermochromic colored dye or pigment in addition to the thermochromic material, and the lightness value (V1) of the color density of the mixed system at the time of color development is 6 or less, The lightness value (V2) is 4 or more and (V2)-(V1)>
The sheet for forming a thermochromic laminate, which is the thermochromic sheet according to item 1, which reversibly changes the color from the metallic luster color of silver to the color of a dye or pigment. 14. A. The optical thickness of the coating layer formed by coating the surface of natural mica with 16 to 39% by weight of titanium oxide is 110 to 170.
a silver metallic luster coloring sheet formed of a silver metallic luster pigment having a particle size of 5 to 100 μm and a resin, and B. (A) A colorless lightness value in a decolored state with a lightness value of 6 or less in a coloration state, which is composed of an electron-donating compound, an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between them. A sheet formed from a thermochromic material having a ratio of 8 or more, and (b) a color-developed state composed of an electron-donating compound, an electron-accepting compound, an organic compound medium that reversibly causes a color reaction between the two, and a synthetic resin. The lightness value of the color density is 6
In the following, the lightness value (V1) of the color density of the mixed system at the time of coloring is 6 in which a colorless thermochromic material having a colorless lightness value of 8 or more in the decolored state and a non-thermochromic colored dye or pigment are blended. A thermochromic sheet selected from the following: a sheet having a color value (V2) of 4 or more and a color value (V2)-(V1)> 1 of a mixed system at the time of erasing, and a thermochromic sheet selected from C.I. The non-thermochromic colored dye or pigment is blended with the synthetic resin so that the lightness value (V3) of the color density is 4 or more, and between the lightness value (V4) at the time of color development of the thermochromic material (V3)- (V
4) A three-color combination sheet for forming a thermochromic laminate that reversibly changes from a metallic luster color of silver to a dye / pigment color, which is a combination of three types of sheets, a coloring sheet and a relationship of> 1. 15. 12. The thermochromic material is a thermochromic material in which microcapsules are encapsulated with an electron-donating compound, an electron-accepting compound, and an organic medium that reversibly causes a color reaction between them.
A combination sheet for forming a thermochromic laminate, which reversibly changes from silver to colorless or to the color of a dye or pigment, as described in any one of 4 above. Regarding

The silver metallic luster pigment used in the present invention is
Specifically, it is a silvery pigment in which the surface of natural mica particles is coated with titanium oxide. The silver metallic luster pigment will be described in more detail. The silver metallic luster pigment is obtained by coating the surface of natural mica particles with 16 to 39% by weight of titanium oxide.
Optical thickness of coating layer 110-170 nm, particle size 5-10
The thickness is 0 μm.

The optical thickness of the coating layer of the present invention means the refractive index ×
The geometrical thickness, which is associated with reflecting certain wavelengths. In other words, a particular optical thickness reflects light of a particular wavelength,
The 110-170 nm titanium oxide layer formed on the surface of natural mica reflects silver-colored light of 380-700 nm. For the thermochromic layer, a heat change material containing three components of an electron-donating color-forming compound, an electron-accepting compound and an organic compound medium that reversibly causes a color reaction is used.

The thermochromic material is most preferably used by being encapsulated in microcapsules. This is because the thermochromic materials can be kept in the same composition under the various use conditions and can exhibit the same effect.

The thermochromic laminate of the present invention comprises a layer in which the aforementioned silver metallic luster pigment and the thermochromic material are bonded together by a transparent film forming material. The lightness value in the present invention is a lightness value of a Munsell color chart system in which, in an achromatic array, perfect black is set to 0, perfect white is set to 10 and the difference between them is equally spaced. The lightness of the chromatic color indicates the lightness value of the achromatic color with which the sense of the brightness of the chromatic color is equal.
That is, the smaller the lightness value is, the closer it is to black, and the larger the lightness value is, the closer it is to white. Therefore, it can be used as an index of how much visible light is absorbed and how much it is reflected. It shows how visible light transmitted through the luster pigment layer is reflected and absorbed by the thermochromic layer below the visible light layer.

[0011]

The heat-modified layered product of the present invention is a layered product in which a silver-colored metallic luster pigment layer is laminated on the thermochromic layer, and the color change of the thermochromic layer is observed through the silver-colored metallic luster pigment layer. It is what makes you see. As mentioned above, when all visible light is reflected, it looks white. In this case, when part of the light of all wavelengths of the incident light is absorbed and the rest is reflected, it becomes dark and becomes gray.

Since the mica is arranged in layers, the reflected light is not diffusely reflected but reflected in the same direction. Such reflected light has a metallic luster. Therefore, the gray with metallic luster becomes silver. In this way, the silver surface of metallic luster is exposed. What is important here is that titanium oxide has an optical thickness of 110
The requirement is ~ 170 nm. If the optical thickness is out of the above range, the wavelength selectivity of reflected light is generated, and the colored light does not become silver.

When a layer containing a non-color-changing dye-pigment colorant is used as the thermochromic layer, a reversible color change from a silver metallic luster color to a colorant color is visually recognized. Since the silver metallic luster pigment layer is transparent, the color of the color-changing layer can be visualized at the same time as the heat-color-changing of the thermochromic layer by disposing the non-color-changing colored layer as the lowermost layer. In the colored state of the thermochromic layer, the underlying non-color-changing colored layer, such as letters and patterns, is also hidden, but at this time, the light-reflecting effect of the silver metallic luster pigment layer makes the concealing effect more than the concealing effect of only the thermochromic layer. Increase. As described above, the thermochromic layer uses three components of an electron-donating color-forming compound, an electron-accepting compound, and an organic compound medium which reversibly causes a color reaction.

Specifically, for example, the above-mentioned Japanese Patent Publication No. 51-35.
No. 414, etc. (1) Three components of (a) an electron-donating color-developing organic compound, (b) a compound having a phenolic hydroxyl group, and (c) a chain type aliphatic monohydric alcohol having no polar substituent are essential components. Reversible thermochromic material. Or (2) (a) an electron-donating color-forming organic compound, (b) a compound having a phenolic hydroxyl group, and (c) an aliphatic monohydric alcohol having no polar substituent and a polar substituent. A reversible thermochromic material containing, as an essential component, three components of a compound selected from an ester having no polar substituent obtained from an aliphatic monocarboxylic acid. Or (3) (a) an electron-donating color-developing organic compound, (b) a compound having a phenolic hydroxyl group, (c) a polar aliphatic substituent-free monohydric alcohol, and a polar substitution Consisting of three components, a compound selected from an aliphatic monocarboxylic acid having no group and an ester having no polar substituent obtained from a chain type aliphatic monohydric alcohol having no polar substituent Reversible thermochromic material. Alternatively, (4) (a) an electron-donating color-developing organic compound, (b) a compound having a phenolic hydroxyl group, (c) a higher aliphatic monohydric alcohol having no polar substituent, and a polar substituent As an essential component, three components of a compound selected from an ester having no polar substituent, which is obtained from a higher aliphatic monocarboxylic acid having no carboxylic acid and a chain aliphatic monohydric alcohol having no polar substituent, Thermochromic material. Etc.

In addition to the above, a thermochromic material containing a thermochromic color-memory dye, which exhibits a large hysteresis characteristic and is discolored, as described in JP-A-60-264285, that is, a change in color density due to temperature change. A type in which the shape of the plotted curve changes color by following a route that differs greatly depending on whether the temperature is raised from the low temperature side of the color change temperature range or is lowered from the high temperature side of the color change temperature range. A thermochromic material is also used, which is characterized in that it can store and retain a state of being changed at a temperature below the low temperature side color changing point or above the high temperature side color changing point in the room temperature range between the low temperature side color changing points. The thermochromic debris body of the present invention will be specifically described.

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

In the laminate of (A) described above, the silver metallic luster pigment layer is a layer in which a silver metallic luster pigment having a particle size of about 5 to 100 μm is fixed to a transparent resin in a dispersed state.
Thermochromic layer, an electron-donating color-changing organic compound, an electron-accepting compound, a thermochromic material consisting of a three-component homogeneous compatible solution of an organic compound medium that reversibly causes the color reaction of the both (hereinafter, A thermochromic material is a thermochromic material having the above-mentioned constitution), and a color changing material composed of a thermochromic material and a transparent film forming material is fixed in a dispersed state. A layer having a colorless lightness value of 8 or more in a color state, and comprising a silver-colored metallic luster-like thermochromic laminate exhibiting a reversible color change from silvery metallic luster color to colorless and colorless to silvery metallic luster color To be done. When the lightness value of the color density in the colored state is 6 or less, it has the ability to sufficiently absorb the light transmitted through the silver metallic luster pigment in the upper layer. For example, in the case of a silver metallic luster pigment, a clear silver metallic Looks shiny. But,
When the lightness value in the color-developed state exceeds 6, the light transmitted through the silver-colored metallic luster pigment cannot be sufficiently absorbed, and a part of the light is also reflected, so that the colored metallic luster color cannot be seen clearly. On the other hand, when the colorless lightness value in the decolored state is 8 or more, it has the ability to sufficiently reflect the light transmitted through the silver metallic luster pigment, so the light reflected by the silver metallic luster pigment and the thermochromic material are reflected. The mixed light mixes and returns to white light,
It doesn't look silvery.

In the laminated body of (B), the silver metallic luster pigment layer is a layer in which a silver metallic luster pigment of about 5 to 100 μm is fixed in a dispersed state on a transparent resin, and the thermochromic layer is the thermochromic layer. Lightness value (V ₁ ) of color density in a color-developed state, in which a color-changing material and a non-color-changing colorant (dye, pigment) are mixed
Is 6 or less, the lightness value (V ₂ ) of the color in the decolored state is 4 or more, and the layer satisfying the relationship of the lightness value (V ₂ ) -lightness value (V ₁ )> 1 is silver. A silver-colored metallic luster tone thermochromic laminate exhibiting a reversible color change from the metallic luster color to the metallic luster color to the silver to metallic luster color is formed. The reason why the lightness value (V ₁ ) of the color density of the color mixture system in the color-developed state is 6 or less is the same as above. On the other hand, the reason why the lightness value (V ₂ ) of the color in the decolored mixed color system is 4 or more and the V ₂ −V ₁ > 1 needs to be satisfied is that the non-color-changing colorant and the non-thermal colorant are used in this system. Since the discoloring dye and pigment are mixed to form a color, the lightness value becomes small and varies depending on the color of the dye or pigment. For example, the lightness value is relatively large for yellow, orange, etc., and conversely, the lightness value is small for red, purple, etc. However, in order to obtain a satisfactory color change, the lightness value in the decolored state needs to be at least larger than 1 in the color development state, and when it is 1 or less, the contrast is too small and the color change occurs. Not clear. If the lightness value is 4 or more under such a condition, for example, a reversible color change from silver to colored or from colored to silver can be exhibited. However, when it is less than 4, the color density of the underlying color mixture layer becomes too high, and the silver color is visible even in the decolored state.

In the laminated body of (C), the lightness value (V ₃ ) of the color density is 4 or more in the lower layer of the thermochromic layer, and between the lightness value (V4) of the coloring state of the thermochromic layer, V3-V4>
The non-discoloring colored layer satisfying the relationship of 1 is formed, and a silver-colored metallic luster-like thermochromic laminate exhibiting a reversible color change between the silver metallic glossy color and the color of the non-discoloring colored layer is formed. It
As described above, the smaller the lightness value when the thermochromic material is emitted or erased, the closer it is to black, and the larger the lightness value is, the closer it is to white. Therefore, how much visible light is absorbed and how much is reflected This index indicates how the visible light transmitted through the silver metallic luster pigment layer is reflected and absorbed by the thermochromic layer below the visible light ray. Therefore, if the thermochromic layer has a lightness value of 6 or less, it has the ability to sufficiently absorb visible light transmitted through the silver metallic luster pigment, and as a result, only the silver light reflected by the silver metallic luster pigment layer is visible. Because you can
It looks silvery. On the contrary, when the brightness value is 8 or more,
Since the visible light that has passed through the silver metallic luster pigment layer is reflected, both the light reflected by the silver metallic luster pigment layer and the light reflected by the thermochromic layer are viewed together, so that the silver color is changed. Disappears.

That is, it is an index of whether or not the thermochromic material has a characteristic of appearing silvery at a temperature lower than the color changing temperature and disappearing the silver color at a temperature higher than the color changing temperature. The brightness value of the present invention is TC-360 manufactured by Tokyo Denshoku Co., Ltd. for the sample prepared as follows.
It is a value obtained by measurement using a 0 color difference meter. 1. Measurement of lightness value of thermochromic layer (including system in which non-color-changing dyes and pigments are mixed) (1) Measurement of lightness value of thermochromic layer (colored ← → colorless) Thermochromic material 10 parts, 50% acrylic acid Ester resin /
45 parts of xylene solution, 20 parts of xylene and 20 parts of methyl isobutyl ketone are stirred and mixed, and spray-painted on a white vinyl chloride sheet having a lightness value of 9.1 with a spray gun to form a thermochromic layer having a thickness of 40 μm after drying. Prepare. The brightness value of the color-developed state and the color-erased state of the obtained thermochromic layer is measured. (2) Measurement of lightness value of thermochromic layer (colored I ← → colored II) 10 parts of thermochromic material, desired amount of non-thermochromic dye / pigment, 50
% Acrylic acid ester resin / xylene solution 45 parts, xylene 20 parts and methyl isobutyl ketone 20 parts by stirring,
After mixing and spray painting on a white vinyl chloride sheet with a brightness value of 9.1 with a spray gun, the thickness after drying is 40 μm.
The thermochromic layer of is prepared. The brightness value of the color-developed state and the color-erased state of the obtained thermochromic layer is measured. 2. Non-discoloring coloring layer (coloring with non-thermo-discoloring dyes and pigments)
Measurement of lightness value of non-thermochromic dye and pigment in a desired amount, 45 parts of 50% acrylic ester resin / xylene solution, 20 parts of xylene and 20 parts of methyl isobutyl ketone are stirred and mixed to obtain a lightness value of 9.1.
Is spray-painted on the white vinyl chloride sheet (1) with a spray gun to prepare a non-discoloring colored layer having a thickness of 10 μm after drying. The brightness value of the obtained non-discoloring colored layer is measured.

Next, a film forming material will be exemplified. Ionomer resin, isobutylene-maleic anhydride resin copolymer resin,
Acrylonitrile-acrylic styrene copolymer resin,
Acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile-chlorinated polyethylene-styrene copolymer resin, ethylene-vinyl chloride copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate-vinyl chloride Graft copolymer resin, vinylidene chloride resin, vinyl chloride resin, chlorinated vinyl chloride resin, vinyl chloride-vinylidene chloride copolymer resin, chlorinated polyethylene resin, chlorinated polypropylene resin, polyamide resin, high density polyethylene resin, medium 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, polymer Rusuchiren resins, polyacrylate resins, polymethyl methacrylate resins, epoxy acrylate resins. Alkylphenol resin, rosin modified phenol resin, rosin modified alkyd resin, phenol 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, unsaturated polyester resin, polyurethane resin, vinyl acetate emulsion resin, styrene-butadiene emulsion resin, acrylic 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 thereof include cellulose derivatives such as cellulose acetate and ethyl cellulose. In the present invention, the above-mentioned resin is called a synthetic resin, and is appropriately selected and applied from the above-mentioned resins according to the purpose. Each layer of the thermochromic laminate of the present invention also 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 phenol resin, rosin-modified alkyd resin, phenol 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, acrylic ester resin, unsaturated polyester resin, polyurethane resin, vinyl acetate emulsion resin, styrene-butadiene emulsion resin, acrylic ester emulsion resin, water-soluble Alkyd resin, water-soluble melamine resin, water-soluble urea resin, water-soluble phenolic resin, water-soluble epoxy resin, water-soluble polybutadiene resin, cellulose derivative and other synthetic resins, and water or organic solvent, etc. Dissolved or dispersed composition is used.

In addition, each layer of the thermochromic laminate of the present invention is
It also includes a molded sheet containing each pigment or thermochromic material. These sheets include ionomer resins of the above film-forming materials, 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 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, polyacrylic ester resin, polymethylmethacrylate resin, epoxy resin, epoxy acrylate resin, alkyd resin, polyurethane resin , Resins etc. are used. The laminate of the present invention may use a sheet and a coating film together. It is preferable to use a transparent resin for the metallic luster pigment layer.
The laminated body can be formed on the surface of the base material, or can be formed as a laminated film-like material not using the base material. As the base material, in addition to various films and sheets, the surface of the molded body itself is used. That is, it is possible to form a thermochromic product on the surface of the molded product to obtain a thermochromic molded product.
As the base material, paper, synthetic paper, cloth, non-woven fabric, synthetic leather, leather, plastic, glass, ceramics, metal, wood, stone, etc. are used. Further, it is not limited to a flat shape, and one having a processed surface such as an uneven shape or a fibrous shape can be used.

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

[0025]

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, in which 1 is a thermochromic laminate comprising two layers. No. 3 has a coating layer in which the surface of natural mica is coated with 29% by weight of titanium oxide and has an optical thickness of 140 nm.
A first layer having a thickness of about 40 μm, which is composed of a silver metallic luster pigment having a particle size of 10 to 60 μm and an acrylic ester resin, and has a function of adjusting the wavelength of reflected light.
4 is incident light, and 5 is reflected light. Of the incident light 4, 6 that has not been reflected is absorbed by the thermochromic layer 2. The thermochromic layer 2 is a thermochromic composition composed 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, an epoxy resin / amine curing agent. A thermochromic material A having an average particle size of 8 μm obtained by microencapsulation by the interfacial polymerization method and having a lightness value of 2.2 when coloring and a lightness value of 9.0 when decoloring. It is a second layer made of an acrylic ester resin and having a thickness of about 40 μm, and reversibly develops and erases colors by heat. When the thermochromic layer develops color at 15 ° C or less and reflects the light 5 which is a part of the visible light of the incident light and absorbs the light 6 having other wavelengths, it becomes a silver metallic luster color and heats at 30 ° C. Discoloration of the discoloration layer, transmitted light 6
Is reflected, all the incident light is reflected, and the silver metallic luster color disappears and becomes colorless. Parts in the above examples are parts by weight. The same applies to the parts in the following examples.

Example 2 In place of 2-anilino-3-methyl-6-dibutylaminofluorane of Example 1, 2-anilino-3-methyl-6 was used.
-Dibutylaminofluorane 1 part, 1,3-dimethyl-
Same as Example 1 except that 2 parts of 6-diethylaminofluorane was used, and a thermochromic material having a lightness value of 2.7 at the time of color development and a lightness value of 8.8 at the time of color erasing prepared in the same manner was used. did. Similarly, below 15 ° C, a silver metallic luster color is obtained,
At 30 ° C. or higher, the silver metallic luster color disappears and it becomes colorless.

Example 3 In place of 2-anilino-3-methyl-6-dibutylaminofluorane of Example 1, 2.5 parts of 2-N, N-dibenzylamino-6-diethylaminofluorane was used. Example 1 was the same as Example 1 except that the prepared thermochromic material having a lightness value of 3.0 during color development and a lightness value of 8.7 during decolorization was used. Similarly, at 15 ° C. or lower, it becomes a silver metallic luster color, and at 30 ° C. or higher, the silver metallic luster color disappears and becomes colorless.

Example 4 In place of 2-anilino-3-methyl-6-dibutylaminofluorane of Example 1, 3- (4-diethylamino-2) was used.
-Ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide (1.5 parts) was prepared in the same manner, and the brightness value at the time of color development was 3.2, and the brightness value at the time of decolorization. Same as Example 1 except that a thermochromic material having a value of 8.7 was used. Similarly, at 15 ° C. or lower, it becomes a silver metallic luster color, and at 30 ° C. or higher, the silver metallic luster color disappears and becomes colorless.

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

Example 6 In the laminate 1 of FIG. 2, the thermochromic layer 7 is composed 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 microencapsulating the thermochromic composition according to claim 1 by an interfacial polymerization method of an epoxy resin / amine curing agent, a fluorescent yellow pigment, and an acrylic ester resin. Which has a lightness value of 2.5 in the mixed system and a lightness value of 8.9 in the case of erasing, and reversibly erases the color by heat and the color of the fluorescent yellow pigment with a thickness of about 40 μm. Is a thermochromic layer,
The silver metallic gloss layer 3 was the same as in Example 1. When the laminated body 1 has a temperature of 15 ° C. or lower, the thermochromic layer develops color, reflects the light 5 which is a part of the visible light of the incident light, and absorbs the light 6 having other wavelengths. When the thermochromic layer disappears at 30 ° C. or higher, the silver metallic luster color disappears and the fluorescent yellow pigment color is obtained. Reference numeral 9 denotes yellow light reflected by the thermochromic layer 7.

Example 7 In the laminate 1 of FIG. 2, the thermochromic layer 7 was 1 part of 2-anilino-3-methyl-6-dibutylaminofluorane,
1,3-dimethyl-6-diethylaminofluorane 2
Part, 6 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 microencapsulating a thermochromic composition by an interfacial polymerization method of epoxy resin / amine curing agent. Approximately 40 μm thick heat-developed color mixture consisting of a thermochromic material, a fluorescent pink pigment and an acrylic ester resin, with a lightness value of 2.3 when coloring and a lightness value of 5.5 when decoloring. Is a thermochromic layer that reversibly erases the color of the fluorescent pink pigment, and the silver metallic gloss layer 3 was the same as in Example 1. The laminate 1 has a silver metallic luster color at 15 ° C. or lower, and disappears at 30 ° C. or higher to have a fluorescent pink pigment color. Reference numeral 9 denotes pink light reflected by the thermochromic layer 7.

Example 8 In the laminate 1 of FIG. 2, the thermochromic layer 7 was formed from 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 microencapsulating the thermochromic composition by an interfacial polymerization method of an epoxy resin / amine curing agent, a fluorescent pink pigment, a blue pigment, and acrylic acid. It is a mixed color of a fluorescent pink pigment and a blue pigment, which is composed of an ester resin and has a lightness value of 2.4 in a mixed system and a lightness value of 5.5 in a decolored state, which is colored by heat and has a thickness of about 40 μm. The silver color metallic luster layer 3 is the same as in Example 1, which is a thermochromic layer that reversibly decolors to the lavender. The laminated body 1 is
At 15 ° C or lower, a silver metallic luster color was obtained, and at 30 ° C or higher, the silver metallic color disappeared and the color became Ravender, which was a mixed color of fluorescent pink pigment and blue pigment. 9 is a thermochromic layer 7
Ravender color light reflected by.

Example 9 In the laminate 1 of FIG. 2, the thermochromic layer 7 was formed from a compatible solution of 3 parts of 2-anilino-3-methyl-6-dibutylaminofluorane, 6 parts of bisphenol A and 50 parts of neopentyl stearate. The thermochromic composition obtained by microencapsulating the thermochromic composition by an interfacial polymerization method of an epoxy resin / amine-based curing agent, the thermochromic material in the form of microcapsules having an average particle diameter of 8 μm, a blue pigment, a white pigment, and an acrylic ester resin. Of a pastel blue, which is a mixed color of a blue pigment and a white pigment and has a lightness value of 2.2 in a mixed system and a lightness value of 5.4 in a decolored color, The silver color metallic luster layer 3 is the same as in Example 1, which is a thermochromic layer that reversibly decolors. The laminate 1 had a silver metallic luster color at 15 ° C. or lower, and had a pastel blue color that was a mixed color of a blue pigment and a white pigment at 30 ° C. or higher. Reference numeral 9 denotes pastel blue color light reflected by the thermochromic layer 7.

Example 10 FIG. 3 shows an example of the present invention, and 2 and 3 are examples 1
However, this example is a thermochromic laminate comprising three layers in which the thermochromic layer 2 and the coloring layer 8 which is the third layer containing a non-thermochromic coloring agent are arranged next to the thermochromic layer 2. . The colored layer 8 is a fluorescent orange layer having a thickness of about 10 μm and made of a fluorescent orange pigment having a brightness value of 6.3 and an acrylic ester resin. The thermochromic layer develops color at 15 ° C or lower, reflects the light 5 which is a part of the visible light of the incident light, and emits the light 6 having other wavelengths.
When the thermochromic layer disappears at 30 ° C. or higher, the silver metallic luster color disappears, and the color becomes the fluorescent orange pigment of the lower layer. 10 is a non-thermochromic colored layer 8
Shows the orange light reflected by.

Example 11 In the colored layer 8 of Example 10, a fluorescent red pigment having a lightness value of 4.7 was used in place of the fluorescent orange pigment, and a lightness value at the time of coloring was 2.2 and at the time of decoloring. A thermochromic composition comprising a compatible solution of 3 parts of 2-anilino-3-methyl-6-dibutylaminofluorane having a lightness value of 9.0, 6 parts of bisphenol A, 25 parts of myristyl alcohol, and 25 parts of cetyl caprate. Average particle size of 8 μm obtained by microencapsulation by the interfacial polymerization method of epoxy resin / amine curing agent
Example 10 was the same as Example 10, except for the second layer having a thickness of about 40 μm, which was composed of a thermochromic material in the form of microcapsules and an acrylic ester resin. The thermochromic layer develops color below 20 ℃,
When the light 5 which is a part of the visible light of the incident light is reflected and the light 6 of other wavelengths is absorbed, it becomes a silver metallic luster color,
When the thermochromic layer is decolored at 20 ° C. or higher, the silver metallic luster color disappears and becomes the color of the fluorescent red pigment in the lower layer. Reference numeral 10 denotes red light reflected by the non-thermochromic colored layer 8.

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

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

Comparative Example 1 The thermochromic material of Example 1 was replaced with a lightness value of 4.
5, 2-anilino-3-having a lightness value of 6.0 when decolorized
A thermochromic composition comprising 6 parts of methyl-6-dibutylaminofluorane, 10 parts of bisphenol A, and 25 parts of neopentyl stearate, which does not become colorless at the time of bleaching, is a microcapsule prepared by interfacial polymerization of an epoxy / amine curing agent. Same as Example 1 except that the thermochromic material in the form of microcapsules having an average particle size of 8 μm obtained by When the temperature is 15 ° C or lower, the thermochromic layer develops color, reflects the light 5 which is a part of the visible light of the incident light, and the light 6 of other wavelengths.
When absorbed, it becomes a silver metallic luster color. In this comparative example, even if the thermochromic layer is decolored at 30 ° C. or higher, since the transmitted light 6 can still be sufficiently absorbed, the silver color is slightly thinned and still looks like a silver metallic luster color.

Comparative Example 2 In the laminate 1 of FIG. 2, the thermochromic layer 7 was 6 parts of 2-anilino-3-methyl-6-dibutylaminofluorane, 10 parts of bisphenol A, neopentyl stearate 25.
Thermochromic material in the form of microcapsules with an average particle diameter of 8 μm obtained by microencapsulating a thermochromic composition that does not become colorless at the time of bleaching, which consists of a compatible solution, by an interfacial polymerization method of an epoxy resin / amine curing agent. And a blue pigment and an acrylic ester resin have a lightness value of 2.
5. A thermochromic layer having a thickness of about 40 μm and a lightness value of 3.3 when decolored, and the silver metallic gloss layer 3 was the same as in Example 1. In this comparative example, even if the thermochromic layer is decolored at 30 ° C. or higher, the transmitted light 6 can still be sufficiently absorbed, so that it is slightly bluish silver and still looks like a silver metallic luster color. .

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

[0041]

INDUSTRIAL APPLICABILITY The thermochromic laminate of the present invention reversibly changes from a silver metallic luster color to a colorless or a non-thermochromic colorant used in combination in accordance with temperature changes. The function of the thermochromic material that has been used is maintained as it is, and the function can be effectively exhibited. That is, in the color change, in a system in which the thermochromic layer is formed of a thermochromic material having an extremely small hysteresis width, the color changes in response to a high sensitivity due to a temperature change,
A system to which a thermochromic material having an intermediate hysteresis width is applied exhibits a response corresponding to a temperature change and discolors. In a system in which the thermochromic layer is formed of a thermochromic material with an extremely large hysteresis width, the changed appearance is maintained in the normal temperature range even after the heat or cold heat required for color change is removed. You can

[Brief description of drawings]

FIG. 1 is an explanatory diagram of a silver-colored thermochromic laminate that 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]

 1 Silver metallic luster thermochromic laminate 2 Thermochromic layer 3 Silver metallic luster layer 4 Incident light 5 Reflected light 6 Transmitted light 7 Thermochromic layer containing nonthermochromic coloring agent 8 Nonthermochromic colored layer 9 Decoloring Light reflected by the thermochromic coloring layer 10 When light is discolored 10 Light reflected by the non-thermochromic colored layer 8

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location B44F 1/08 9134-3K C09D 5/38 PRF 7211-4J D02G 3/06 // C09C 1/40 PBB 6904- 4J C09D 5/00 PSD 6904-4J

Claims (15)

[Claims] 1. A. 16-39% by weight on the surface of natural mica
The optical thickness of the coating layer coated with titanium oxide is 110 to
B. a first layer of waste, which is 170 nm and has a particle size of 5 to 100 μm, which comprises a silver-colored metallic luster pigment and a film-forming material for adjusting the wavelength of reflected light; A thermochromic material comprising an electron-donating compound, an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between the both, and a colorless lightness in a decolored state with a lightness value of 6 or less in a colored state. A layer formed of a thermochromic material having a value of 8 or more and a film forming material was used as a second layer,
A thermochromic laminate that reversibly changes from a silver metallic luster color to colorless. 2. A. The first layer is (a) 1 on the surface of natural mica.
The coating layer coated with 6 to 39% by weight of titanium oxide has an optical thickness of 110 to 170 nm and a particle size of 5 to 100 μm.
16 to 39 weight of the silver metallic luster color coating layer formed by coating the coating composition comprising the silver metallic luster pigment of m, the coating film forming material and the colorant, and (b) the surface of the natural mica. % Titanium Oxide Coating Optical Layer Thickness 110-170
nm and a particle size of 5 to 100 μm, a silver metallic luster coloring sheet formed by a silver metallic luster pigment and a synthetic resin,
A layer for adjusting the wavelength of the reflected light selected from and B. The second layer is a thermochromic material comprising (a) an electron-donating compound, an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between the two, and the lightness value of the color density in the colored state is 6 or less. A layer formed by coating a coating composition comprising a thermochromic material having a colorless lightness value of 8 or more in a decolored state, a coating film forming material and a color developing agent, and (b) an electron donating compound and an electron accepting property. A thermochromic material comprising a compound and an organic compound medium that reversibly causes a color reaction between the both, and a thermochromic material having a color density of 6 or less in a colored state and a colorless brightness value of 8 or more in a decolored state. The thermochromic laminate which reversibly changes from a silver metallic luster color to colorless, according to claim 1, which is a thermochromic layer selected from a material and a thermochromic sheet formed of 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. The color brightness value (V2) of the mixed system at the time of erasing is 4 or more (V2)
-(V1)> 1, as described in claim 1 or 2,
A thermochromic laminate that reversibly changes from a silver metallic luster color to a dye / pigment color. 4. The thermochromic layer of the thermochromic laminate according to claim 1, which reversibly changes from a silver metallic luster color to a colorless or dye / pigment color. Between the non-thermochromic colored dye or pigment and the lightness value (V3) of the color density formed by the film forming material is 4 or more and the lightness value (V4) at the time of color development of the thermochromic material (V3 )-(V
4) A thermochromic laminate in which a non-thermochromic dye / pigment coloring layer is arranged, which satisfies the relationship of 1>, and which reversibly changes from a silver metallic luster color to a dye / pigment color. 5. The thermochromic material is a thermochromic material in which microcapsules are encapsulated with an electron-donating compound, an electron-accepting compound, and an organic medium that reversibly causes a color reaction between them.
A thermochromic laminate according to any one of items 1 to 4, which reversibly changes from a silver metallic luster color to a colorless or dye / pigment color. 6. A heat powder obtained by cutting a thermochromic laminate, which reversibly changes from a silver metallic luster color to a colorless color or a dye / pigment color according to claim 1, and is pulverized. Discolorable granular material. 7. A thermochromic laminate, which is reversibly discolored from a metallic luster color of silver to colorless or a color of a dye or pigment according to claim 1, is cut into a thread shape. Discolorable thread. 8. A. 16-39% by weight on the surface of natural mica
The optical thickness of the coating layer coated with titanium oxide is 110 to
A coating composition comprising a silver metallic luster pigment having a particle size of 5 to 100 μm and a coating film-forming material and a color developer; The lightness value of the color density in the colored state is 6 or less and the colorless lightness value in the decolored state is 8 or more, which is composed of an electron-donating compound, an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between them. A thermochromic laminate that reversibly changes from a silver metallic luster color to a colorless color by combining two types of coating compositions, a thermochromic material, a coating composition comprising a film-forming material, and a color-developing agent. Two-component coating composition for body formation. 9. A lightness value (V1) of a color density of a mixed system at the time of color development in which a coating composition comprising a thermochromic material, a film forming material and a colorant is mixed with a non-thermochromic colored dye or pigment. ) Is 6
The reversibly silvery color according to claim 8, which is a thermochromic composition having a color value (V2) of 4 or more and a color value of (V2)-(V1)> 1 in the mixed system at the time of erasing. A two-pack type composition for forming a thermochromic laminate, which changes from the metallic luster color of the above to the color of a dye or pigment. 10. A. The optical thickness of the coating layer obtained by coating the surface of natural mica with 16 to 39% by weight of titanium oxide is 110.
A coating composition comprising a silver metallic luster pigment having a particle size of 5 to 100 μm and a particle size of 5 to 100 μm, a coating film forming material, and a color developing agent; (A) Colorless lightness value in a decolored state with a lightness value of 6 or less in a coloration state, which is composed of an electron-donating compound, an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between them. Having a value of 8 or more, a coating composition comprising a thermochromic material, a film-forming material and a color-developing agent, and (b) an organic compound that reversibly causes a color reaction between the electron-donating compound and the electron-accepting compound. A thermochromic material having a color density of 6 or less in a color-developed state and a colorless brightness value of 8 or more in a decolorized state, a film-forming material, and a non-thermochromic colored dye comprising a compound medium. Alternatively, the lightness value (V1) of the color density of the mixed system at the time of color development containing a pigment is 6 or less, and the lightness value (V) of the mixed system at the time of decolorization (V
2) is 4 or more and (V2)-(V1)> 1 coating composition, and a thermochromic composition selected from C.I. Between the lightness value (V3) of the color density formed by the non-thermochromic dye or pigment, the coating film forming material and the color developing agent is 4 or more, and the lightness value (V4) at the time of color development of the thermochromic material. To (V
3)-(V4)> 1 is established, and a non-thermochromic dyeing / pigment coloring coating composition, which is a reversible silver metallic luster color in combination with three types of overcoating coating compositions. A three-pack type coating composition for forming a thermochromic laminate that changes its color. 11. The thermochromic material according to claim 8, wherein the thermochromic material comprises an electron-donating compound, an electron-accepting compound, and an organic medium that reversibly causes a color reaction between the both, encapsulated in microcapsules. A liquid coating composition for forming a thermochromic laminate, which reversibly changes from a silver metallic luster color to a colorless or dye / pigment color described in any one of items. 12. A. The optical thickness of the coating layer obtained by coating the surface of natural mica with 16 to 39% by weight of titanium oxide is 110.
A silver metallic luster coloring sheet formed of a resin and a silver metallic luster pigment having a particle size of 5 to 100 μm and a particle size of 5 to 100 μm; The lightness value of the color density in the colored state is 6 or less and the colorless lightness value in the decolored state is 8 or more, which is composed of an electron-donating compound, an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between them. A sheet for forming a thermochromic laminate, which reversibly changes from a metallic luster color of silver to colorless, which is a combination of two types of sheets, which are a thermochromic material and a thermochromic sheet formed of a resin. 13. A thermochromic sheet containing a non-thermochromic colored dye or pigment in addition to the thermochromic material and having a lightness value (V1) of color density of 6 or less in a mixed system at the time of color development, The color brightness value (V2) of the mixed system is 4 or more and (V2)-
(V1)> 1 which is a thermochromic sheet, wherein the thermochromic laminate-forming sheet reversibly changes from a silver metallic luster color to a dye / pigment color. 14. A. The optical thickness of the coating layer obtained by coating the surface of natural mica with 16 to 39% by weight of titanium oxide is 110.
A silver metallic luster coloring sheet formed of a resin and a silver metallic luster pigment having a particle size of 5 to 100 μm and a particle size of 5 to 100 μm; (A) A colorless lightness value in a decolored state with a lightness value of 6 or less in a coloration state, which is composed of an electron-donating compound, an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between them. A sheet formed from a thermochromic material having a ratio of 8 or more, and (b) a color-developed state composed of an electron-donating compound, an electron-accepting compound, an organic compound medium that reversibly causes a color reaction between the two, and a synthetic resin. The lightness value of the color density is 6
In the following, the lightness value (V1) of the color density of the mixed system at the time of coloring is 6 in which a colorless thermochromic material having a colorless lightness value of 8 or more in the decolored state and a non-thermochromic colored dye or pigment are blended. A thermochromic sheet selected from the following: a sheet having a color value (V2) of 4 or more and a color value (V2)-(V1)> 1 of a mixed system at the time of erasing, and a thermochromic sheet selected from C.I. The non-thermochromic colored dye or pigment is blended with the synthetic resin so that the lightness value (V3) of the color density is 4 or more, and between the lightness value (V4) at the time of color development of the thermochromic material (V3)- (V
4) A three-color combination sheet for forming a thermochromic laminate that reversibly changes from a metallic luster color of silver to a dye / pigment color, which is a combination of three types of sheets, a coloring sheet and a relationship of> 1. 15. The thermochromic material according to claim 12, wherein the thermochromic material comprises an electron-donating compound, an electron-accepting compound, and an organic medium that reversibly causes a color reaction between the both, in a microcapsule. A thermochromic laminate forming combination sheet reversibly changing from silver to colorless or to the color of a dye or pigment, as described in any one of items.