JPH061067A - Thermal discoloring laminate and composition and sheet used for manufacturing the laminate - Google Patents

Abstract

PURPOSE:To obtain a laminate reversibly changing from gold color to a colorless state by using a layer consisting of a gold metallic gloss pigment and a film forming material and adjusting the wavelength of refleced 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 lightness 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 gold metallic gloss pigment, in which the optical thickness of a coating layer, in which the surface of natural mica is coated with 41-44wt.% titanium oxide, is 180-240nm and grain size is 5-60mum, 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 is employed as a second layer 2. Accordingly, a laminate thermally discolored from a gold color to a colorless state reversibly can be obtained.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to a golden metallic luster thermochromic laminate and coating compositions and sheets used to form the laminate. More specifically, the present invention relates to a metallic luster-like thermochromic laminate that exhibits a color change from gold to color change and a coating composition and a sheet used for forming the laminate.

[0002]

2. Description of the Related Art Conventionally, thermochromic materials exhibiting a reversible color change of colored ← → colorless and colored [1] ← → colored [2] due to temperature change 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 golden 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. Other attempts to diversify color changes are disclosed in Japanese Utility Model Publication No. 3-14400. 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, since liquid crystals are essentially colorless and reflect a specific wavelength that is selective scattering of visible light, a blackish opaque layer is required on the back surface, and therefore the color change is black-red-yellow-green-blue. -Purple-
Since it looks black, the color change is not clear even if a pearlescent layer is provided on it. For example, when a golden pearl luster pigment is used, the color change is golden-golden red-golden yellow-golden green-golden blue-golden purple-golden, giving a clear gold color. It does not show a change to a non-tinted 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. The golden color is the most luxurious color and the change from the golden color attracts the most attention from the viewer, so there was a great demand for changing the color of the golden color to another color.

[0004]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The inventors of the present invention have conducted research to effectively exhibit the color-changing effect of a thermochromic material and to change the color of gold metallic luster in a vivid and colorful manner 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. Therefore,
By stacking a gold metallic luster pigment layer on the colored-colorless thermochromic layer of the thermochromic material, a colorless color change can be visualized from the golden metallic luster color. Therefore, for example, by providing a colored-colorless thermochromic layer on a white support and laminating a gold metallic luster pigment layer on the thermochromic layer, it is possible to visualize a white color change from a golden metallic luster color. I can. It is also possible to make the viewer visually recognize a clear color change from a golden metallic luster color to a color by mixing a non-discoloring 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 golden 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.

[0005]

According to the present invention, there is provided "1. A. The optical thickness of a coating layer in which the surface of natural mica is coated with 41 to 44% by weight of titanium oxide having an optical thickness of 180 to 240.
a layer for adjusting the wavelength of reflected light, which is composed of a golden metallic luster pigment having a particle size of 5 to 60 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 and which reversibly changes from a metallic metallic color of gold to colorless. 2. A. The first layer is (a) 41-44 on the surface of natural mica.
The optical thickness of the coating layer coated with 1% by weight of titanium oxide is 1
A golden metallic luster color coating layer formed by coating a coating composition comprising a golden metallic luster pigment having a particle size of 80 to 240 nm and a particle size of 5 to 60 μm, a coating film forming material and a color developing agent;
(B) A gold color formed by a synthetic metallic resin and a golden metallic luster pigment having an optical thickness of 180 to 240 nm and a particle size of 5 to 60 μm, in which the surface of natural mica is coated with 41 to 44% 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. The thermochromic laminate which reversibly changes from a metallic luster color of gold to colorless, 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 is reversibly changed from a golden metallic luster color to a dye / pigment color according to item 1 or 2, wherein 1 >> 1. 4. The thermochromic layer of the thermochromic laminate, which reversibly changes from a metallic luster color of gold to colorless or a color of a dye or pigment, according to any one of 1 to 3 is followed by a non-thermochromic layer. (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 laminated body in which a non-thermochromic dye / pigment coloring layer is arranged and a reversible gold metallic luster color is changed to a dye / pigment color. 5. Gold metallic luster pigment 30-48 on the surface of natural mica
The optical thickness of the coating layer coated with 4 wt% of titanium oxide and 4-10 wt% of iron oxide is 140-240.
A metallic metallic luster pigment having a size of 5 nm and a particle size of 5 to 60 μm. The heat that reversibly changes from a metallic metallic luster color of golden color described in any one of Items 1 to 4 to a pale yellow or dye / pigment color. Discolorable laminate. 6. Gold metallic luster pigment 30-48 on the surface of natural mica
Gold metal luster having a particle size of 5 to 60 μm and an optical layer thickness of 140 to 240 nm coated with 0.5% to 10% by weight of titanium oxide and further coated with 0.5 to 10% by weight of non-thermochromic colored dyes and pigments. A thermochromic laminate, which is a pigment and reversibly changes from the metallic luster color of gold to the color of a nonthermochromic dye / pigment according to any one of 1 to 4. 7. 7. The thermochromic material is a thermochromic material in which microcapsules are encapsulated in an organic medium that reversibly causes a color reaction between an electron-donating compound and an electron-accepting compound, and the thermochromic material is any one of 1 to 6. The thermochromic laminate that reversibly changes color from gold to colorless to pale yellow or to the color of dye / pigment. 8. A thermochromic granular material obtained by cutting and powdering a thermochromic laminate which is reversibly discolored from a metallic metallic color of gold to colorless or a color of a dye or pigment described in any one of 1 to 7. 9. A thermochromic yarn which is formed into a thread by cutting the thermochromic laminate, which reversibly changes from a metallic luster color of gold to colorless or a color of a dye or pigment described in any one of 1 to 7. 10. A. The optical thickness of the coating layer in which the surface of natural mica is coated with 41 to 44% by weight of titanium oxide is 180 to 240.
coating composition comprising a golden metallic luster pigment having a particle size of 5 to 60 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 material, a film-forming material and a color-developing agent,
A two-component coating composition for forming a thermochromic laminate, which reversibly changes from a golden metallic luster color to colorless, by combining two types of coating compositions consisting of 11. 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. A thermochromic composition having a mixed lightness value (V2) of 4 or more at the time of erasing and (V2)-(V1)> 1.
A two-pack coating composition for forming a thermochromic laminate, which reversibly changes from a metallic luster color of gold to a color of a dye or pigment. 12. A. The optical thickness of the coating layer in which the surface of natural mica is coated with 41 to 44% by weight of titanium oxide is 180 to 240.
coating composition comprising a golden metallic luster pigment having a particle size of 5 to 60 μm, a coating film-forming material, and a colorant, and B. (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. When a non-thermochromic colored dye or pigment is added to a thermochromic material having a color density of 6 or less and a colorless luminosity value of 8 or more in the decolorized state, which comprises a compound medium, A coating composition having a lightness value (V1) of the color density of the mixed system of 6 or less and a colored lightness value (V2) of the mixed system at the time of erasing of 4 or more and (V2)-(V1)>1; A thermochromic coating 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 satisfied, and a non-thermochromic dyeing / pigment coloring coating composition, which is a reversible gold 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. 13. 10. 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 liquid coating composition for forming a thermochromic laminate, which reversibly changes from a gold color to a colorless to pale yellow color or a dye / pigment color, according to any one of 2 items. 14. A. The optical thickness of the coating layer in which the surface of natural mica is coated with 41 to 44% by weight of titanium oxide is 180 to 240.
a metallic metallic luster color sheet having a particle size of 5 to 60 μm and a metallic metallic luster pigment formed of a synthetic 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 that reversibly changes color from a metallic luster color of gold to colorless, which is a combination of two types of sheets, which are a thermochromic material and a thermochromic sheet formed of a synthetic resin. 15. 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 metallic luster color of gold to the color of a dye or pigment. 16. A. The optical thickness of the coating layer in which the surface of natural mica is coated with 41 to 44% by weight of titanium oxide is 180 to 240.
a metallic metallic luster color sheet having a particle size of 5 to 60 μm and a metallic metallic luster pigment formed of a synthetic 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-kind combination sheet for forming a thermochromic laminate, which is a combination of three types of sheets, a coloring sheet and a relationship of> 1, and which reversibly changes from a metallic luster color of gold to a color of a dye or pigment. 17. 14. 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 a gold color to a colorless to pale yellow color or a dye / pigment color according to any one of 6 items. Regarding

The golden metallic luster pigment used in the present invention is
Specifically, it is a pigment having a gold color in which the surface of natural mica particles is coated with titanium oxide. Further, a golden metallic luster pigment in which the surface of natural mica particles is coated with titanium oxide and the upper layer thereof is coated with iron oxide is also used. In addition, a dichroic metallic luster pigment obtained by coating a titanium oxide coating with a non-thermochromic colored dye / pigment is also used. More specifically, the golden metallic luster pigment is a golden metallic luster pigment in which the surface of natural mica particles is coated with 41 to 44% by weight of titanium oxide, the optical thickness of the coating layer is 180 to 240 nm, and the grain size is 5 nm. ˜60 μm, or the surface of natural mica particles is coated with 30-48 wt% titanium oxide, and the upper layer is coated with 4-10 wt% iron oxide, the optical thickness of the coating layer is 140-240 nm,
The surface of a golden metallic luster pigment having a particle size of 5 to 60 μm or natural mica particles was coated with 30 to 48% by weight of titanium oxide, and the upper layer thereof was coated with 0.5 to 10% by weight of a non-thermochromic colored dye / pigment. Optical thickness of coating layer 140-240 nm, particle size 5
A dichroic golden metallic luster pigment having a thickness of up to 60 μm can also be used.

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,
Optical thickness of coating layer formed on the surface of natural mica 180-
The 240 nm titanium oxide layer reflects the gold light of 550 to 600 nm. For the thermochromic layer, a thermochromic 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.

When a layer containing a non-discoloring dye / pigment colorant is used as the thermochromic layer, a reversible color change from a metallic metallic color of gold to a color of the colorant is visually recognized. Since the golden metallic luster pigment layer is transparent, the color of the colored layer can be visualized at the same time as the thermal discoloration of the thermochromic layer by disposing the noncolor-changing colored layer as the lower layer. When the non-thermochromic coloring layer is arranged as the lowermost layer, the lower non-color-changing colored layer such as letters and designs is hidden in the colored state of the thermochromic layer, but at this time, the light reflection of the golden metallic luster pigment layer is caused. The effect enhances the hiding effect as compared to the hiding effect of only thermal discoloration. 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 respective layers in which the above-mentioned golden metallic luster pigment and the thermochromic material are bonded together by a transparent film forming material.

In the arrangement of achromatic colors, the brightness value of the thermochromic material at the time of emitting and erasing is 0 for perfect black and 10 for perfect white, and the difference in the sense of brightness between them is equal. The lightness value of the Munsell color chart system thus divided is shown, and the lightness of the chromatic color shows the lightness value of the achromatic color having the same sense of brightness as the chromatic color. 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.

[0010]

The heat-modified layered product of the present invention is a layered product in which a golden metallic luster pigment layer is laminated on the thermochromic layer, and the color change of the thermochromic layer is observed through the golden metallic luster pigment layer. It is what makes you see. Here, the property of the golden metallic luster pigment, that is, the selective interference of the wavelength of visible light due to the fact that the surface of the natural mica particles is 41 to 44% by weight and the optical thickness is 180 to 240 nm. By the synergistic effect of the iris effect, the transmission effect, and the effect of reflecting and absorbing visible light of the lightness value of the thermochromic layer, the multicolored change of the metallic luster of gold is visualized. Specifically, the 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 and the thickness of the coating layer within the above range. For example, selectively reflect yellow light,
The optical thickness of the coating layer is 180-
When the lower layer of the titanium oxide-coated mica prepared to have a thickness of 240 nm is black, the violet light that is transmitted is absorbed by the lower layer of black, and only the yellow light of 550 to 600 nm is reflected.
It has a golden color. On the other hand, when the lower layer is white, the transmitted violet light is also reflected by the lower white, and not only the yellow light but also the violet light is reflected, and all wavelengths of visible light are reflected. It Therefore, by reversibly changing the lower thermochromic layer to black ← → white, it is possible to make the viewer visually see a reversible color change of gold ← → white.

What is important here is that titanium oxide must meet the requirement of an optical thickness of 180 to 240 nm. If the optical thickness is out of the above range, the reflected light is not light having a wavelength of 550 to 600 nm and does not become golden.

Furthermore, in the case of the golden metallic luster pigment in which the surface of the natural mica particles is coated with titanium oxide and the upper layer thereof is coated with iron oxide, in addition to the above wavelength-selective reflection and transmission effects, iron oxide itself has By incorporating the characteristics of absorbing violet light and reflecting yellow light, a reversible color change from brighter gold to pale yellow is visualized. However, since the iron oxide itself is colored in pale yellow, the coating layer looks pale yellow even if the base is white. When the coverage of titanium oxide is less than 30% by weight, it is difficult to obtain a sufficient golden color. Therefore, in order to obtain a golden color, it is necessary to coat more than 10% by weight with iron oxide. Even if the color changes, the metallic luster layer always exhibits a golden color, and a clear color change cannot be obtained. Further, when the coverage of titanium oxide exceeds 48% by weight, the color of light that is selectively reflected is not yellow, so even if it is subsequently coated with iron oxide, a beautiful golden color is not obtained. When the iron oxide coverage is less than 4% by weight, the effect of iron oxide shown above does not sufficiently appear, and when it exceeds 10% by weight, it becomes a golden color, but metallic luster even if the thermochromic material discolors. The layer is always golden and no clear color change is obtained.

When iron oxide is also used, forming an iron oxide film on the titanium oxide film is most effective for developing a golden metallic luster color. When titanium oxide is coated on iron oxide, the effect of titanium oxide is large and the effect of iron oxide is small. When titanium oxide and iron oxide are mixed, iron oxide may be present in the upper layer, but titanium oxide may block the reflected light of iron oxide, resulting in poor iron oxide reflection efficiency. When an iron oxide film is provided on top of the titanium oxide film, the iron oxide layer has the property of absorbing purple light and reflecting other light, and this light appears to be yellow, so the titanium oxide layer has a metallic luster. It has the effect of adding depth. This is because the iron oxide film as the upper layer prevents the reflected light from this iron oxide layer from being interrupted or reflected by other layers.

In the case of a golden 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 colored dye / pigment, the color of the non-thermochromic colored dye / pigment to be coated is It is possible to express a wider variety of colors by using, for example, a black ← → white thermochromic layer in combination with gold ← → pink, gold ← → blue, etc. You can visualize the target color change. When the coverage of titanium oxide is less than 30% by weight, it is difficult to obtain a sufficient golden color. Therefore, when the non-thermochromic colored dye / pigment is coated, it does not look golden. Also, the titanium oxide coverage is 4
If it exceeds 8% by weight, the color of light that is selectively reflected is not yellow, so that it does not look golden. When the coverage of the non-thermochromic colored dye / pigment is less than 0.5% by weight, a sufficient color density of color cannot be obtained. When it exceeds 10% by weight, the color density of the color is too high, and the gold color cannot be expressed. When each of the pigments is within the above range, it is possible to impart the characteristic of selectively transmitting the light of the wavelength of gold color and reflecting the light of the wavelength of the complementary color relationship. If it is out of the above range, the wavelength selectivity is lost, or the wavelength selectivity is present but the color is not golden.

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, it is described in, for example, Japanese Patent Publication No. 51-35414. (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. Alternatively, (3) (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 Three components of a compound selected from any one of an aliphatic monocarboxylic acid having no substituent and an ester having no polar substituent obtained from a chain type aliphatic monohydric alcohol having no polar substituent are essential components. And a reversible thermochromic material containing this in microcapsules. 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 Three components of a compound selected from a polar substituent-free ester obtained from a higher aliphatic monocarboxylic acid having no substituent and a chain aliphatic monohydric alcohol having no polar substituent are used as essential components. , A thermochromic material obtained by dissolving or dispersing this in a vehicle. Etc.

In addition to this, a thermochromic material containing a color memory memorable thermochromic dye, which exhibits a large hysteresis characteristic and is discolored as described in JP-A-60-264285, that is, a plot of change in color density due to temperature change is plotted. The type of discoloration in which the shape of the curved line changes its color by following a route that is significantly different when the temperature is raised from the lower temperature side than the color change temperature range and when it is lowered from the higher temperature side than the color change temperature range. A thermochromic material is also used, which has a characteristic that it can 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 a room temperature range between the low temperature side color changing points.

Next, the thermochromic laminate of the present invention will be specifically described. The thermochromic laminate of the present invention includes the following laminates (A) to (C). (A) A laminate in which a gold-colored metallic luster pigment layer is laminated on the thermochromic layer. (B) A laminate in which a gold metallic luster pigment layer is laminated on a thermochromic layer formed by mixing a thermochromic material with a non-chromic dye. (C) A laminate in which a thermochromic layer is laminated on the non-color-changing colored layer, and a gold 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 golden metallic luster pigment layer,
A transparent protective film may be laminated on the upper side of the golden metallic luster pigment layer. Next, the gold metallic luster thermochromic laminate of the present invention will be described based on the above (A) to (C).

In the layered product (A) described above, the golden metallic luster pigment layer is a layer in which a golden metallic luster pigment having a particle size of about 5 to 60 μm is fixed to a transparent resin in a dispersed state, and the thermochromic layer is , An electron-donating color-developing organic compound, an electron-accepting compound, and a thermochromic material comprising a three-component homogeneous compatible solution of an organic compound medium that reversibly causes a color reaction between the both (hereinafter, thermochromic material A layer having a lightness value of color density of 6 or less in a colored state and a colorless lightness value of 8 or more in a decolored state, which is fixed in a dispersed state by a transparent film forming material. A golden metallic luster tone thermochromic laminate exhibiting a reversible color change from a golden metallic luster color to colorless and a colorless to golden metallic luster color is constituted. When the lightness value of the color density in the color-developed state is 6 or less, it has the ability to sufficiently absorb the light that has passed through the gold metallic luster pigment in the upper layer. Looks shiny. However, if the lightness value in the color-developed state exceeds 6, the light transmitted through the golden metallic luster pigment cannot be sufficiently absorbed and a part of the light is reflected again, so that the metallic luster color cannot be clearly seen. 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 golden metallic luster pigment, so that the light reflected by the golden metallic luster pigment and the thermochromic material are reflected. The mixed light mixes back to white light and appears colorless. However, when the lightness value in the decolored state is less than 8, the light transmitted through the golden metallic luster pigment cannot be sufficiently reflected and partially absorbed, so that the light does not become colorless and the golden metallic color in the colored state remains. .

In the layered product (B), the golden metallic luster pigment layer is a layer in which a metallic luster pigment of about 5 to 60 μm is fixed to a transparent resin in a dispersed state, and the thermochromic layer is
The thermochromic material and the non-discoloring colorant, such as a dye or a pigment, are mixed, and the lightness value (V ₁ ) of the color density in the colored state is 6
Hereinafter, a layer having a color lightness value (V ₂ ) in the decolored state of 4 or more and satisfying a relationship of (V2)-(V1)> 1 is described below. A golden metallic luster thermochromic laminate is formed which exhibits a reversible color change of the golden metallic luster color. 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 above V ₂ −V ₁ > 1 needs to be satisfied is that in this system, a non-discoloring colorant, that is, a non-discoloring colorant is used. Since the thermochromic 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 conditions, for example, a reversible color change from gold to colored or from colored to golden can be exhibited. However, if it is less than 4, the color density of the underlying color mixture layer becomes too high and the transmitted light is absorbed, so that the gold color is visible even in the decolored state.

In the laminate of (C), the lightness value of the color density (V ₃ ) is 4 or more in the lower layer of the thermochromic layer, and between the lightness value (V ₄ ) of the coloring state of the thermochromic layer. , _V 3 _-V 4>
The non-discoloring colored layer satisfying the relationship of 1 is formed, and a gold metallic glossy thermochromic laminate showing a reversible color change between the gold 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, the lightness value absorbs visible light and to what extent. It shows whether the light is reflected or not, and how the visible light transmitted through the gold metallic luster pigment layer is reflected / absorbed by the thermochromic layer located thereunder. 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 golden metallic luster pigment, and as a result, only the yellow light reflected by the golden metallic luster pigment layer is visible. Because it can, it looks golden. On the other hand, when the lightness value is 8 or more, the visible light transmitted through the golden metallic luster pigment layer is reflected, so that the yellow light reflected by the golden metallic luster pigment layer and the light reflected by the thermochromic layer are reflected. Both of them will be viewed together, so they will not look golden. That is, the lightness value is an index of whether or not the thermochromic material has a characteristic of appearing golden below the color change temperature and disappearing above the color change temperature.

The lightness value of the present invention is a value obtained by measuring the sample prepared as follows using a TC-3600 color difference meter manufactured by Tokyo Denshoku Co., Ltd. 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 for this layer 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, chlorine 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 Rate resins, polycarbonate resins, polystyrene resins, high impact polystyrene resins, polypropylene resins, polymethyl styrene resins, polyacrylate resins, polymethyl methacrylate resin,
Epoxy acrylate resin. Alkylphenol resin,
Rosin modified phenolic resin, rosin modified alkyd resin,
Phenol resin modified alkyd resin, epoxy resin modified alkyd resin, styrene modified alkyd resin, acrylic modified alkyd resin, amino alkyd resin, vinyl chloride-vinyl acetate resin, styrene-butadiene resin, epoxy resin, unsaturated polyester resin, polyurethane resin, acetic acid Vinyl 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. Cellulose derivatives such as cellulose acetate, nitrate cellulose, ethyl cellulose and the like can be mentioned. 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 Resins such as water-soluble alkyd resin, water-soluble melamine resin, water-soluble urea resin, water-soluble phenol resin, water-soluble epoxy resin, water-soluble polybutadiene resin, and cellulose derivative are dissolved in water or organic solvent and other color-developing agents. Composition dispersed is used.

In addition, each layer of the thermochromic laminate of the present invention comprises
A molded sheet in which each pigment or thermochromic material is mixed with a synthetic resin is also included. 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 low density polyethylene resin, linear low density polyethylene resin, polyethylene Rephthalate resin, polybutylene terephthalate resin, polycarbonate resin, polystyrene resin, high impact polystyrene resin, polypropylene resin, polymethylstyrene resin, polyacrylic ester resin, polymethylmethacrylate resin, epoxy resin, epoxyacrylate resin, alkyd resin, polyurethane resin , And other resins are used. A sheet and a coating film may be used together to form a laminate. It is preferable to use a transparent resin for the metallic luster pigment layer. The laminate can be formed on the surface of the base material, or can be formed as a laminate without using the base material.

As the base material, in addition to various films and sheets, the surface of the molded product itself is used. In other words, a thermochromic laminate can be formed on the surface of the molded product to form a thermochromic molded product. The base material is paper, synthetic paper, cloth, non-woven fabric,
Synthetic leather, leather, plastic, glass, ceramics, metal, wood, stone, etc. are used. Also, not limited to a flat shape,
It is also possible to use those having a processed surface such as irregularities and fibrous shapes. The laminate is formed by a conventionally known method, for example, screen printing, offset printing, gravure printing, coater, tampo printing, printing means such as transfer, brush coating, spray coating, electrostatic coating, electrodeposition coating, 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, ultraviolet absorbers, infrared absorbers, antioxidants, singlet oxygen quenchers, anti-aging agents, antistatic agents, polarity imparting agents, thixotropic agents, defoamers, stabilizers, plasticizers, flame retardants, Additives such as extender pigments, lubricants, and foaming agents can be added to each layer such as a metallic luster pigment layer and a thermochromic layer, if necessary.

[0026]

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 had a surface of natural mica coated with 43% by weight of titanium oxide and had an optical thickness of 210 nm and a particle size of 1
A first layer having a thickness of about 40 μm, which is composed of a gold metallic luster pigment having a thickness of 0 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, the light 6 that has not been reflected is absorbed by the thermochromic layer 2. Thermochromic layer 2
Is a thermochromic composition comprising a compatible solution of 2-anilino-3-methyl-6-dibutylaminofluorane (3 parts), bisphenol A (6 parts) and neopentyl stearate (50 parts) as 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 by microencapsulation according to 1., the lightness value during color development is 2.2, and the lightness value during decolorization is 9.
It is a second layer having a thickness of about 40 μm and made of a thermochromic material of 0 and an acrylic ester resin, and reversibly develops and erases colors by heat. The thermochromic layer develops color at 15 ° C. or lower, reflects light 5 having a wavelength of 550 to 600 nm, which is a part of incident light, and absorbs light 6 having other wavelengths, resulting in a golden metallic luster color. When the thermochromic layer is decolored at .degree. C. and the transmitted light 6 is reflected, all the incident light is reflected, and the golden metallic luster color disappears and becomes colorless. The 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-
Similarly prepared using 2 parts of 6-diethylaminofluorane, the lightness value at the time of color development is 2.7, and the lightness value at the time of decolorization is 8.
Same as Example 1 except that the thermochromic material of No. 8 was used. Similarly, at 15 ° C. or lower, a golden metallic luster color was obtained, and at 30 ° C. or higher, the golden metallic luster color disappeared to become colorless.

Example 3 Coloring was similarly prepared, using 1.5 parts of 6-diethylamino-benzo (a) -fluorane instead of 2-anilino-3-methyl-6-dibutylaminofluorane of Example 1. Example 1 was the same as Example 1 except that a thermochromic material having a brightness value of 4.0 and a brightness value of 8.9 was used.
Similarly, at 15 ° C or lower, a golden metallic luster color is obtained,
Above 0 ° C, the golden metallic luster color disappeared and became colorless.

Example 4 Instead 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 was used in the same manner as above, but the brightness value at the time of color development was 3.2, and the color value was similarly erased. The same as Example 1 except that a thermochromic material having a lightness value of 8.7 was used. Similarly, at 15 ° C. or lower, a golden metallic luster color was obtained, and at 30 ° C. or higher, the golden metallic luster color disappeared to become colorless.

Example 5 Instead of the golden metallic luster pigment of Example 1, the surface of natural mica was coated with 42% by weight of titanium oxide, and further 2.5% by weight.
Coated with navy blue has an optical thickness of 210 nm and a grain size of 1
Same as Example 1 except that a gold metallic luster pigment of 0 to 50 μm was used. Similarly, at 15 ° C. or lower, a golden metallic luster color was obtained, and at 30 ° C. or higher, the golden metallic luster color disappeared to become blue.

Example 6 FIG. 2 shows an example of the present invention, in which 3 is a surface of natural mica coated with 36% by weight of titanium oxide and further 8% by weight of iron oxide at an optical thickness of 200 nm. Particle size is 10-6
A first layer having a thickness of about 40 μm, which is composed of a 0 μm golden metallic luster pigment and an acrylic ester resin. No. 7 has a lightness value of 2.5 when the mixed system is colored, and a lightness value of 8.9 when the color is erased.
Of the thermochromic material, the non-thermochromic fluorescent yellow pigment, and the acrylic ester resin used in Example 1, which are reversibly colored by heat and decolorized to the color of the fluorescent yellow pigment with a thickness of about 40 μm. This is the second layer to be performed. The thermochromic layer develops color at 15 ° C or less, and is 550 to 600 nm which is a part of incident light.
When the light of wavelength 5 is reflected and the light 6 of wavelengths other than that is absorbed, it becomes a golden metallic luster color. When the thermochromic layer is decolored at 30 ° C or higher, the metallic metallic luster color disappears and the fluorescent yellow pigment It becomes a color. Reference numeral 9 is yellow light reflected by the thermochromic layer 7.

Example 7 In the laminate 1 of FIG. 2, the thermochromic layer 7 was 2-anilino-3-methyl-6-dibutylaminofluorane 1 part,
1,3-dimethyl-6-diethylaminofluorane 2
Part, bisphenol A 6 parts, neopentyl stearate 50 parts by thermo-chromic composition obtained by microencapsulation by an interfacial polymerization method of epoxy resin / amine curing agent in the form of microcapsules having an average particle size of 8 μm. 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 golden metallic gloss layer 3 was the same as in Example 1. Similarly, below 15 ° C, a golden metallic luster color is obtained,
With the above, the golden metallic luster color disappears and becomes the color of the fluorescent pink pigment. 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. It was a thermochromic layer for reversibly decoloring to the lavender, and the golden metallic luster layer 3 was the same as in Example 1. Similarly, at 15 ° C. or lower, it becomes a golden metallic luster color, and at 30 ° C. or higher, the golden metallic luster color disappears and becomes a Ravender color which is a mixed color of a fluorescent pink pigment and a blue pigment. Reference numeral 9 indicates Ravender color light reflected by the thermochromic layer 7.

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, 5 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 blue pigment, a white pigment, and an acrylic ester. Pastel blue, which is a mixed color of a blue pigment and a white pigment, which has a lightness value of 2.2 in the color development of a mixed system and a lightness value of 5.4 in the decolorization and is formed by heat and has a thickness of about 40 μm It is a thermochromic layer for reversibly decoloring, and is a golden metallic luster layer 3
Was the same as in Example 1. Similarly, at 15 ° C. or lower, it becomes a golden metallic luster color, and at 30 ° C. or higher, the golden metallic luster color disappears and becomes a pastel blue color which is a mixed color of a blue pigment and a white pigment. Reference numeral 9 denotes pastel blue color light reflected by the thermochromic layer 7.

Embodiment 10 FIG. 3 is an embodiment of the present invention, and 2 and 3 are Embodiment 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. . In this embodiment, 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 lightness value of 6.3 and an acrylic ester resin. The thermochromic layer develops color at 15 ° C. or lower, reflects light 5 having a wavelength of 550 to 600 nm, which is a part of incident light, and absorbs light 6 having other wavelengths, resulting in a golden metallic luster color. When the thermochromic layer disappears at temperatures above ℃, the golden metallic luster color disappears and becomes the color of the fluorescent orange pigment in the lower layer. Reference numeral 10 denotes orange light reflected by the colored layer 8.

Example 11 In the coloring 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 the lightness value at the time of coloring the thermochromic layer was 2.2. Thermal discoloration consisting of a compatibilized solution of 3 parts of 2-anilino-3-methyl-6-dibutylaminofluorane, 6 parts of bisphenol A, 25 parts of myristyl alcohol, and 25 parts of cetyl caprate having a lightness value of 9.0 when decolorized. Of a thermochromic material 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 and an acrylic ester resin layer having a thickness of about 40 μm. Same as Example 10 except that it was replaced. The thermochromic layer develops color at 20 ° C. or lower, and is 550 to 600 n which is a part of incident light.
When the light 5 of m wavelength is reflected and the light 6 of other wavelengths is absorbed, it becomes a golden metallic luster color. When the thermochromic layer is decolored at 20 ° C or higher, the metallic metallic luster color disappears and the fluorescence of the lower layer is lost. It becomes the color of the red pigment. Reference numeral 10 represents red light reflected by the colored layer 8.

Example 12 The same as Example 11 except that in the colored layer 8 of Example 11, a fluorescent pink pigment having a lightness value of 5.6 was used in place of the fluorescent red pigment. Similarly, the thermochromic layer develops a color at 20 ° C. or lower, and a part of the incident light is 550 to 600 n.
When the light 5 of m wavelength is reflected and the light 6 of other wavelengths is absorbed, it becomes a golden metallic luster color. When the thermochromic layer is decolored at 20 ° C or higher, the metallic metallic luster color disappears and the fluorescence of the lower layer is lost. It became the color of pink pigment. 10 indicates pink light reflected by the colored layer 8.

Example 13 Example 13 was the same as Example 10 except that in the colored layer 8 of Example 11, a fluorescent green pigment was used instead of the fluorescent orange pigment. Similarly, the thermochromic layer develops color at 20 ° C. or lower, and is 550 to 600 nm which is a part of incident light.
When the light of wavelength 5 is reflected and the light of wavelengths other than 6 is absorbed, it becomes a golden metallic luster color. When the thermochromic layer disappears at 20 ° C or higher, the metallic metallic luster color disappears and the lower fluorescent green It became the color of the pigment. Reference numeral 10 represents green light reflected by the 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 which does not become colorless at the time of bleaching and which is composed of a compatible solution of 6 parts of methyl-6-dibutylaminofluorane, 10 parts of bisphenol A and 25 parts of neopentyl stearate, is microcapsules prepared by interfacial polymerization of an epoxy / amine curing agent. Example 1 was the same as Example 1 except that the thermochromic material in the form of microcapsules having an average particle size of 8 μm obtained by the above-mentioned method was used. At 15 ° C. or lower, the thermochromic layer develops color, reflects light 5 having a wavelength of 550 to 600 nm, which is a part of incident light, and absorbs light 6 having other wavelengths, resulting in a golden metallic luster color. In this comparative example, even if the thermochromic layer is discolored at 30 ° C. or higher, since the transmitted light 6 can still be sufficiently absorbed, the gold color is slightly thinned and still looks like a golden metallic luster color.

Comparative Example 2 Instead of the fluorescent yellow pigment of Example 6, a blue pigment having a lightness value of 2.5 in the color development of the mixed system and a lightness value of 3.3 in the color erasure of the mixed system was used. Example 6 was the same as Example 6 except that a thermochromic layer having a thickness of about 40 μm made of a color-changing material, a blue pigment and an acrylic ester resin was used. Similarly, at 15 ° C. or lower, the thermochromic layer develops color, which is 550 to 60 which is a part of the incident light.
When the light 5 having a wavelength of 0 nm is reflected and the light 6 having other wavelengths is absorbed, a metallic metallic color of gold is obtained. 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 is a slightly bluish gold color and still looks like a golden metallic luster color. .

Comparative Example 3 Instead of the fluorescent orange pigment of Example 10, a red pigment was used.
Example 10 was the same as Example 10 except that the red pigment layer of the coloring layer 8 having a lightness value of 3.7 was used. Similarly, at 15 ° C. or lower, the thermochromic layer develops color, and 550 to 550 which is a part of the incident light.
When the light 5 having a wavelength of 600 nm is reflected and the light 6 having other wavelengths is absorbed, a metallic metallic color of gold is obtained. In this comparative example, even if the thermochromic layer is discolored at 30 ° C. or higher, since the transmitted light 6 can still be sufficiently absorbed, it becomes a slightly reddish gold color and still looks like a golden metallic luster color. .

[0042]

INDUSTRIAL APPLICABILITY The thermochromic laminate of the present invention reversibly changes its color from a metallic metallic color of gold to a colorless or non-thermochromic colorant used in combination with a change in temperature. In the present invention, the function of the thermochromic material used is maintained as it is, and the function can be effectively exhibited. That is, in the above-mentioned 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 temperature with high sensitivity, and a thermochromic material having an intermediate hysteresis width is applied. In this system, the color changes with a corresponding response to the temperature change. 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 gold-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 Gold metallic luster thermochromic laminate 2 Thermochromic layer 3 Gold 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 layer 7 at the time of 10 Light reflected by the non-thermochromic layer 8 at the time of decoloring

Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location B32B 33/00 7141-4F B44F 1/08 9134-3K C09C 1/40 PBB 6904-4J D02G 3/06 D21H 19 / 80 19/38 27/02 7199-3B D21H 5/02 7211-4J C09D 5/38 PRF

Claims (17)

[Claims] 1. A. 41-44% by weight of the surface of natural mica
The optical thickness of the coating layer coated with titanium oxide is 180-
A layer that is 240 nm and has a particle size of 5 to 60 μm and that adjusts the wavelength of reflected light, which is composed of a golden metallic luster pigment 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 and which reversibly changes from a metallic metallic color of gold to colorless. 2. A. The first layer is (a) 4 on the surface of natural mica.
The coating layer coated with 1 to 44% by weight of titanium oxide has an optical thickness of 180 to 240 nm and a particle size of 5 to 60 μm.
41 to 44% by weight of a gold metallic luster color coating layer formed by coating a coating composition consisting of the golden metallic luster pigment, a coating film forming material and a colorant, and (b) the surface of natural mica. The optical thickness of the coating layer coated with titanium oxide is 180-240n
m, and a layer for adjusting the wavelength of reflected light selected from a golden metallic luster pigment having a particle size of 5 to 60 μm and a golden metallic luster coloring sheet formed of a synthetic resin, 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 metallic luster color of gold to colorless, according to claim 1, which is a layer which undergoes a thermocolor change 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 golden metallic luster color to a dye / pigment color. 4. A thermochromic layer of the thermochromic laminate according to any one of claims 1 to 3, which reversibly changes from a metallic luster color of gold to a colorless or 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 is reversibly changed from a metallic metallic color of gold to a dye / pigment color. 5. A gold metallic luster pigment is applied on the surface of natural mica.
It is coated with 0 to 48% by weight of titanium oxide and 4 to 10 on it.
The optical thickness of the coating layer coated with wt% iron oxide is 140
It is a metallic luster pigment of golden color having a particle size of 5 to 60 μm and having a particle size of ˜240 nm, and reversibly changes from a metallic luster color of golden color to a pale yellow color or a color of dye / pigment according to any one of claims 1 to 4. Thermochromic laminate. 6. A gold metallic luster pigment is applied on the surface of natural mica.
Coated with 0-48% by weight of titanium oxide, on which 0.5
The coating layer coated with 10% by weight of the non-thermochromic colored dye / pigment has an optical thickness of 140-240 nm and a particle size of 5-60.
A thermochromic laminate that reversibly changes from a gold metallic luster color to a color of a non-thermochromic dye / pigment according to any one of claims 1 to 4, which is a gold metallic luster pigment of µm. 7. 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.
7. A thermochromic laminate according to any one of items 1 to 6, which reversibly changes color from gold to colorless to pale yellow or to a dye or pigment color. 8. A heat powder obtained by cutting a thermochromic laminate, which reversibly changes from a metallic luster color of gold to a colorless color or a color of a dye or pigment, according to claim 1 to powder. Discolorable granular material. 9. A thermosensitive color-changing laminate, which reversibly changes from a metallic luster color of gold to colorless or a color of a dye or pigment, according to claim 1, is cut into a thread shape. Discolorable thread. 10. A. The optical thickness of the coating layer obtained by coating the surface of natural mica with 41 to 44% by weight of titanium oxide is 180.
A coating composition comprising a golden metallic luster pigment having a particle size of 5 to 60 μm and a particle size of 5 to 60 μm, a coating film forming material, and a color developing agent; 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 material, a film-forming material and a color-developing agent,
A two-component coating composition for forming a thermochromic laminate, which reversibly changes from a golden metallic luster color to colorless, by combining two types of coating compositions consisting of 11. 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 coating film forming material and a colorant is mixed with a non-thermochromic colored dye or pigment. ) Is 6 or less, and the color brightness value (V2) of the mixed system at the time of erasing is 4 or more, and the reversible composition according to claim 10, which is a thermochromic composition of (V2)-(V1)> 1. A two-pack type coating composition for forming a thermochromic laminate, which changes from a metallic metallic color of gold to a color of a dye / pigment. 12. A. The optical thickness of the coating layer obtained by coating the surface of natural mica with 41 to 44% by weight of titanium oxide is 180.
A coating composition comprising a golden metallic luster pigment having a particle size of 5 to 60 μm and a particle size of 5 to 60 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. When a non-thermochromic colored dye or pigment is added to a thermochromic material having a color density of 6 or less and a colorless luminosity value of 8 or more in the decolorized state, which comprises a compound medium, A coating composition having a lightness value (V1) of the color density of the mixed system of 6 or less and a colored lightness value (V2) of the mixed system at the time of erasing of 4 or more and (V2)-(V1)>1; A thermochromic coating 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 satisfied, and a non-thermochromic dyeing / pigment coloring coating composition, which is a reversible gold 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. 13. The thermochromic material according to claim 10, 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 microcapsules. The liquid coating composition for forming a thermochromic laminate, which reversibly changes from a gold color to a colorless to pale yellow color or a dye / pigment color according to any one of the items. 14. A. The optical thickness of the coating layer obtained by coating the surface of natural mica with 41 to 44% by weight of titanium oxide is 180.
A golden metallic luster coloring sheet formed of a synthetic metallic resin and a golden metallic luster pigment having a particle size of 5 to 60 μm and having a particle size of ˜240 nm; 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 that reversibly changes color from a metallic luster color of gold to colorless, which is a combination of two types of sheets, a thermochromic material and a thermochromic sheet formed of synthetic resin. 15. A thermochromic sheet containing a non-thermochromic colored dye or pigment in addition to a thermochromic material and having a lightness value (V1) of a color density of a mixed system at the time of color development of 6 or less, The color brightness value (V2) of the mixed system is 4 or more and (V2)-
The sheet for forming a thermochromic laminate, which is a thermochromic sheet of (V1)> 1 and reversibly changes from a metallic luster color of gold to a color of a dye or pigment according to claim 14. 16. A. The optical thickness of the coating layer obtained by coating the surface of natural mica with 41 to 44% by weight of titanium oxide is 180.
A golden metallic luster coloring sheet formed of a synthetic metallic resin and a golden metallic luster pigment having a particle size of 5 to 60 μm and having a particle size of ˜240 nm; (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 by 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 non-thermochromic colored dye or pigment is blended in addition to the thermochromic material having a colorless lightness value of 8 or more in the decolored state. In the following, a thermochromic sheet selected from a sheet having a color lightness value (V2) of 4 or more at the time of erasing and (V2)-(V1)> 1, and a C.I. (V3) -between the lightness value (V4) of the color density obtained by blending a non-thermochromic colored dye or pigment in the synthetic resin with a synthetic resin and at least 4 (V4)- (V
4) A three-color combination sheet for forming a thermochromic laminate, which is a combination of three types of sheets, a coloring sheet and a relationship of 1>, and which reversibly changes color from a metallic luster color of gold to a color of dye / pigment. 17. The thermochromic material according to claim 14, 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 microcapsules. A combination sheet for forming a thermochromic laminate, which reversibly changes from a gold color to a colorless to pale yellow color or a dye / pigment color according to any one of the items.